Orihime Inoue (井上 織姫 Inoue Orihime?) is a classmate and friend of Ichigo Kurosaki, the main character of the series. Like many other friends of Ichigo, she quickly develops spiritual powers of her own after Ichigo becomes a Soul Reaper. Through the series, Orihime learns about Ichigo's duties as a Soul Reaper and decides to accompany him when he goes to Soul Society to save Rukia Kuchiki. She also has a crush on Ichigo, which becomes love as the series continues, but has problems in confessing such feelings.
Orihime's power manifests itself as the Shun Shun Rikka (盾舜六花?, literally "six flowers of the shielded hibiscus", translated in the English anime as "six princess-shielding flowers"), six fairy-like creatures that reside in her hair-clips (shaped like six-petaled flowers, each fairy is two points on a given clip) when inactive.
The fairies are separate manifestations of Orihime's spirit, each with its own unique appearance and personality, and each named after a flower. Orihime's techniques involve incantations manipulating the Shun Shun Rikka into three different groups. Though Orihime initially needed to chant an incantation to use her techniques, further training has rendered this unnecessary. Her incantation consists of voicing the names of the members involved, followed by the technique name and the phrase "I reject" (私は拒絶する watashi wa kyozetsu suru?), a reference to the nature of her powers. The only limit that has been shown to Orihime's power is her own confidence; any self-doubt weakens her abilities and can cause them to fail.
Santen Kesshun (三天結盾?, literally "triple heavenly linking shield") is Orihime's defensive technique. The incantation arranges Baigon, Hinagiku and Lily into a triangle, forming a barrier capable of repelling anything seen so far.
Koten Zanshun (孤天斬盾?, literally "solitary heavenly cutting shield") is Orihime's offensive technique. The incantation summons Tsubaki (椿鬼?), who forms a thin barrier on either side of himself that cuts through enemies like a sword. However, when Tsubaki is destroyed by an arrancar, Orihime is unable to use this technique until Tsubaki is revived. Koten Zanshun is the least effective of Orihime's abilities, not because of any lack of power, but because her own pacifist nature. Since the technique is invariably lethal if effective, Orihime is conflicted about whether she truly wants it to work, and thus any powerful foe can block the attack.
Sōten Kisshun (双天帰盾?, literally "twin heavenly returning shield") is Orihime's healing technique, though it goes well beyond simple healing. The incantation summons Shun'ou and Ayame to form a half-oval barrier around whatever or whomever Orihime wishes. While active, the barrier repels all negative events inflicted upon anything within the barrier. No matter how extensive the damage may be (whether used on living beings or inanimate objects), the barrier can restore it to full working order by reversing space and time around the damaged area, making it as if the object was never damaged in the first place. This is the aspect of her power that piques Sōsuke Aizen's interest in her since, in Aizen's words, she "violates the realm of gods.

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Yasutora Sado (茶渡 泰虎 Sado Yasutora^?) is a teenager who studies in the same class as Ichigo Kurosaki. Because Ichigo first read Yasutora's name off a nametag, he pronounced hisfamily name as Chad (チャド Chado^?) due to the variable pronunciations of kanji, and Ichigo continues to call him this throughout the story. When first introduced, Chad had no special powers aside from his unusual strength and endurance. After his encounter with the cockatiel containing the soul of Yūichi Shibata, he starts to detect the approximate locations of spirits and hollows, but cannot fully see them. Only after saving Karin Kurosaki from a hollow, during the hollow-slaying match between Uryū and Ichigo, did Chad begin to fully see spirits. At the same time that he becomes able to clearly see spirits, he also awakes his latent spiritual ability, which manifests as armor on his right arm called the Brazo Derecha [sic] de Gigante (巨人の右腕（ブラソ・デレチャ・デ・ヒガンテ） Buraso Derecha De Higante^?, Spanish for "right arm of the giant". Japanese for "giant's right arm").Chad's armor increases his strength beyond its already impressive level, and enables him to fire powerful energy blasts from his fist. After training with Renji, Chad gains an improved version of his armored arm. He also gains a new special attack called El Directo (巨人の一撃（エル・ディレクト）Eru Direkuto^?, Spanish for "the direct". Japanese for "giant's strike". "Directo" is the Spanish term for 'jab' in boxing.) To perform it, the flanges on Chad's arm open up and he punches the enemy.

While in Hueco Mundo, Chad states that his powers are closer to that of a hollow's and that they were affected by the environment, allowing him to more deeply tap his powers, which manifest as armor on both arms, instead of just his right. In addition, he also gains the ability to move at high speeds in a manner similar to flash steps and sonido. Chad's full-powered right arm is still called the Brazo Derecha de Gigante but is now used for defense instead of offense (though it's still more powerful offensively than his original arm). Brazo Derecha de Gigante becomes a shield that extends from his hand to some distance beyond his forearm with the same intricate pattern as before. Chad's armored left arm, used for attack, is known as the Brazo Izquierda [sic] del Diablo (悪魔の左腕（ブラソ・イスキエルダ・デル・ディアボロ） Buraso Isukieruda Deru Diaboro^?, Spanish for "left arm of the devil". Japanese for "Devil's left arm"). With this arm, Chad gains a special attack known as La Muerte (魔人の一撃（ラ・ムエルテ） Ra Muerute^?, Spanish for "the death," Japanese for "devil's strike"), a powerful fist containing energy from all his fingers.

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Uryū Ishida (石田 雨竜 Ishida Uryū^?, rendered as "Uryū" in the Viz Media manga and "Uryu" in the Viz Media anime and Bleach: The 3rd Phantom) is introduced in the series as a classmate of the Soul Reaper Ichigo Kurosaki, who reveals himself to be a Quincy, a clan of humans which was destroyed by the Soul Reapers. Wanting to prove the Quincies were better, Uryū challenges Ichigo to see who could kill more Hollows. However, once they are overpowered and start working together, they start knowing each other, to the point they become friends. Since then, Uryū appears in the series as an ally from Ichigo, accompanying him in every fight he has.

When first introduced, Uryū uses the most common ability from the Quinces: a bow named Lone Sparrow (弧雀 Kojaku^?), which has a basic form and a luminescent. Being made of free-flowing spirit particles, its size can be affected the amount of spirit particles and spiritual pressure available to it, as seen in his interaction with Ichigo during his first encounter with a Menos Grande. Additionally, he is able to use many Quincy techniques and items to augment his abilities, including some high-level techniques, which are rare enough that even Mayuri Kurotsuchi, who had studied 2661 Quincy, had never seen them in person.

As preparation for his travel to Soul Society, Uryū later masters the sanrei glove, greatly increasing his abilities via a form of resistance training. In this state, Uryū's bow is solid and covered in an intricate pattern. This new bow allows Uryū to fire several shots simultaneously. By removing the glove, Uryū attains the Quincy Final Form. The Quincy Final Form gives him a vast increase in power, enough to defeat a captain-class Soul Reaper with ease. As a result of removing the glove, however, the Quincy Final Form uses too much power for Uryū's body to handle, causing his body to block his Quincy powers completely after it wears off.

After Uryū regains his powers with the aid of his father, he uses a new Quincy cross, this one resembling a pentancle, and a variant of his original bow called Lone Sparrow on a Silver Cliff(銀嶺弧雀 Ginrei Kojaku^?). Unlike his original bow, this bow is shaped like a spiderweb and can fire up to 1,200 shots at once. Uryū also steals a set of Seele Schneiders (魂を切り裂くもの（ゼーレシュナイダー Zēre Shunaidā^?, German and Japanese for "soul cutter"), special arrows which can be used as swords. Seele Schneiders can also be used in a reiatsu-based pentacle with the target at the center. Upon receiving Uryū's spiritual energy, it explodes, a technique called Sprenger. Uryū can also use a special Quincy foot technique calledHiyrenraku, which is similar to the Soul Reaper's shunpo and the arrancar's sonido.

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Renji Abarai (阿散井 恋次 Abarai Renji^?) is the lieutenant of the 6th Division in the Gotei 13 under captain Byakuya Kuchiki. Renji's zanpakutō is Zabimaru (蛇尾丸^?, roughly "snake tail"). Zabimaru is a nue (a baboon with a snake tail), hence his name. Zabimaru's spirit is portrayed as battle-loving and proud, similar in personality to Renji. Both the snake and baboon are capable of speaking, though the baboon is usually the more dominant one.

Zabimaru's shikai command is "howl" (咆えろ hoero^?), although in the English adaptation of the anime the term used is "roar". In such state, it transforms into a segmented blade with a pick-like protrusion on each segment. The segments are connected by a stretchable thread, making Zabimaru more useful as a whip than an actual sword. While Zabimaru can be stretched to incredible lengths in its whip form, Renji has a limit of three consecutive attacks before having to bring the segments of Zabimaru back together for recovery. Renji can also use his spiritual power to separate the segments and surround an opponent with them, allowing him to execute a one-shot omnidirectional attack called higa zekkō (狒牙絶咬^?, "bite of a baboon's broken fang").

Zabimaru's bankai is Hihiō Zabimaru (狒狒王蛇尾丸^?, "baboon king snake tail") and transforms Zabimaru into a massive version of its shikai form resembling a skeletal snake. Unlike its shikai, Zabimaru's segments are held together by Renji's spiritual power, allowing him to separate and reattach them at will. Even if a segment is damaged, Renji can simply detach it and reform Zabimaru. Zabimaru itself, in bankai form, does not literally "cut", Renji usually catches his opponent with the snake-head of his weapon and smashes his opponent into the ground with it. Zabimaru also gains a special technique known as hikōtsu taihō (狒骨大砲^?, "baboon bone cannon") after Renji becomes more adept with using his bankai. The technique fires a dense blast of spiritual energy from Zabimaru's mouth. He can also use a much more powerful higa zekkō, where all the segments detach and sharpen using spiritual energy.

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Byakuya Kuchiki (朽木 白哉 Kuchiki Byakuya^?) is the captain of the 6th Division in the Gotei 13. His lieutenant is Renji Abarai. He's also the most important person in the Kuchiki Clan. Byakuya first appears on a mission with his lieutenant, Renji Abarai, to capture Rukia Kuchiki and kill Ichigo Kurosaki. They succeed in retrieving Rukia, and would have easily killed Ichigo, if not for Rukia's intervention, pleading for Byakuya not to give the finishing blow. Byakuya later interrupts Ganju Shiba and Hanatarō Yamada's attempt to rescue Rukia and, later on, Renji's attempt. When Ichigo succeeded in rescuing Rukia, he and Byakuya have an extended battle, where both use their bankai. However, Ichigo's inexperience with his new release and Byakuya switching to a more powerful form leaves Ichigo at a disadvantage. It was through the temporary emergence of Ichigo's inner hollow that evened the odds out once more.

Byakuya, as the 6th Division Soul Reaper captain, is skilled in all forms of Soul Reaper combat. In keeping with his rank, Byakuya's abilities allow him to defeat opponents of lieutenant level Soul Reaper without much effort.

Of particular note is Byakuya's speed: he is skilled in the use of flash steps, having trained with (but never surpassed) Flash Master Yoruichi Shihōin. Yoruichi also taught Byakuya some techniques of her own creation involving flash steps, including one called utsusemi (空蝉, lit. empty cicada, in reference to their molting), which allows Byakuya to move out of harm's way while leaving an afterimage behind. One of Byakuya's favorite techniques, as described by Renji, is senka (闪花, lit. Flash Blossom), a flash step combined with a spin to quickly move behind the enemy, followed by a combination of two quick thrusts. In his battle with Zommari Leroux, he is able to maintain his composure and fight at full speed, despite being forced to cut the tendons in one of his legs and arms to prevent Zommari from gaining control of them.

Byakuya has also displayed knowledge of high level kidō spells, able to cast spells up to number 81 without the incantation. He is adept at using them strategically, such as disrupting the movement of Renji's bankai with a well-timed fire spell and damaging Ichigo's right arm by using a low-level lightning spell at point-blank range to burn a hole through his shoulder.

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Gin Ichimaru (市丸 ギン Ichimaru Gin^?) is the captain of the 3rd Division in the Gotei 13 until he betrays Soul Society, and after that he becomes a commander inSōsuke Aizen's arrancar army. His lieutenant was Izuru Kira. Gin's most distinguishing characteristic is his expression; with his slitted eyes and ever-present grin, his face looks like that of a fox. Ichigo derisively nicknames him "fox-face" in their first meeting because of this (in the English dub, he instead replies with a more generalized insult). He also has unusual silver hair, which has a purple tint to it in the anime; his name refers to his hair color, gin (銀, "silver"). Gin rarely removes his smile or opens his eyes; his eyes open when he is significantly annoyed or angry.

Gin Ichimaru's zanpakutō is Shinsō (神鎗^?, literally "Divine spear"). It takes the form of a wakizashi when sealed. The guard is shaped like an 'S'. Shinsō's shikai is triggered by the phrase "shoot to kill" (射殺せ ikorose^?); in the anime, this was slightly changed to the declarative ikorosu. In the English translation of the series, the phrase is inconsistent between uses, but mostly describes stabbing (slay, impale, pierce). Another trigger phrase, used in the first Soul Society arc, was "Shoot 'em dead". Its first rendering in the Viz translation was "skewer that punk". In its shikai, Shinsō's blade glows white and extends at high speed to impale Gin's opponents. In addition to making it a deadly long-range weapon, the extending blade also carries tremendous force without affecting Gin, making it useful for dislodging heavy objects, as seen when Gin pushes bothIchigo Kurosaki and the giant Jidanbō out from under the Seireitei gate, despite Jidanbō being firmly braced under it. Once extended, Gin can maintain the blade's length and swing Shinsō in wide arcs, simultaneously attacking multiple targets with speed and ease. While it has not been seen in the actual series, various Bleach console games have depicted Shinsō as having additional abilities. In Bleach: The Blade of Fate, Bleach: Dark Souls, and Bleach: Shattered Blade, Gin fires Shinsō into the sky and swords similar to Shinsō's unreleased state rain all around him. In Bleach: Blade Battlers Gin shoots Shinsō into the ground and the blade hits the opponent from underneath, whereas in Bleach: Heat the Soul 5, a wave of blades instead shoots up from the ground to hit the opponent.

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Kenpachi Zaraki (更木 剣八 Zaraki Kenpachi) is the captain of the 11th Division within the Gotei 13. His lieutenant is Yachiru Kusajishi. Prior to entering the Soul Reaper ranks, Zaraki resided in District 80, the most lawless district surrounding Soul Society. He became very proficient with swordsmanship while he was there; or at least fighting, and eventually adopting the district's name, "Zaraki", as his surname. After leaving the district he found a small girl who, despite her young age, did not fear his sword. Since she had no name, he named her Yachiru (やちる) in remembrance of the only person he ever admired. At the same time he also took on a name for himself: Kenpachi, the title bestowed upon the strongest swordsman, the one who has killed the most, and a tradition amongst captains of the 11th Division. Yachiru became inseparable from Zaraki from that point further, following him wherever he went, usually clinging to his back.

Kenpachi is the only captain of the Gotei 13 who doesn't know the name of his sword, nor can he use his bankai as a result. In addition, he never uses kidō and rarely uses flash steps. The Bleach Official Bootleg databook ranks his talent in the former as zero. However, he more than makes up for his faults in sheer power. His spiritual pressure is such that, even when wearing the energy-sealing eyepatch, Kenpachi can fight on-par with and defeat other captain-level opponents, even when they release their zanpakutō in either shikai or bankai form. Its concentration is so great that it acts like armor against weaker opponents. During their first duel, he allowed Ichigo one free attack before the duel began. That attack failed to pierce his body, and Ichigo's right hand was wounded in the process. By releasing the bulk of his spiritual pressure, he was also able to cancel out the strongest attack of Maki Ichinose's Nijigasumiduring their battle in the Bount Arc. Despite his seeming disregard for any strategy in his fights and his self-admitted aversion to thinking during battle, Kenpachi is adept at finding and exploiting weaknesses in his opponents' techniques. While he claims to have no sanity or common sense, Kenpachi is actually very perceptive and notices traits in people that others wouldn't notice. For example, he correctly singles out Kaname Tōsen and Gin Ichimaru as the only captains who are afraid to die. During his battles with both Kaname Tōsen and Nnoitra Jiruga, he formulates strategies to work around his disadvantages, such as losing most of his senses or fighting an opponent with six arms. Kenpachi has tremendous quantities of physical strength, proving able to both kick Tōsen through a building in their battle, and grab Ichigo's giant sword barehanded to reel both him and it in for an attack. His physical strength is matched by his endurance; Kenpachi has been shown to easily ignore most of the injuries he sustains in battle, not suffering any debilitation despite suffering multiple lacerations that would disable normal humans. He even allowed himself to be stabbed just to grab Tōsen's blade and break his bankai's effect. The majority of his fight with Nnoitra was a one-sided brawl in Nnoitra's favor, with Kenpachi only taking things seriously when he finds himself in actual danger of dying from the sheer number of lacerations he had received. Kenpachi was proven strong enough to stop Nnoitra's Cero with his bare hands, effortlessly, without showing any sign of injury in the process.

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Tōshirō Hitsugaya (日番谷 冬獅郎 Hitsugaya Tōshirō^?) is the captain of the 10th Division in the Gotei 13. His lieutenant is Rangiku Matsumoto. Hitsugaya is the lead character of theBleach-based film The DiamondDust Rebellion. Tōshirō Hitsugaya is very young by Soul Society standards. Born in Rukongai, he became the youngest ever to reach captain rank. Thus, he is called a "boy genius" or a "child prodigy" by many. Hitsugaya is generally mature and serious, in contrast to his free-spirited lieutenant, Rangiku Matsumoto, although he can sometimes be short-tempered and irritable. Despite their personality differences, he and Matsumoto seem to be very close. Hitsugaya is shown to also be easily irked by others goofing off or drawing unneeded attention to themselves, as shown when he led a team of Soul Reapers into Ichigo Kurosaki's school. He hates anything that he deems childish and hates being described as something close to a child, evident in a filler episode when he meets Ichigo's sister, Karin, who pats him over the head further angering him. This is also shown more in the omake chapters, where he is repeatedly mistaken for a child, much to his annoyance.

Hitsugaya's zanpakutō is Hyōrinmaru (氷輪丸^?, literally "ice ring", idiomatically "full moon"). Hyōrinmaru's shikai command is translated in the English anime as "sit upon the frosted heavens" or "reign over the frozen heavens" (霜天に坐せ sōten ni zase^?). Hyōrinmaru is the strongest of all ice element zanpakutō in Soul Society. Hyōrinmaru's spirit is a large, winged, Chinese dragon. Hyōrinmaru allows Hitsugaya to control water and ice. The slashes created by Hyōrinmaru gives off an immense amount of spirit power which overflows from the tip of the blade, creating a flow of ice vaguely shaped like Hyōrinmaru's dragon spirit. The dragon flies at opponents and instantly freezes anything it touches. The chain-blade also freezes anything Hitsugaya traps with it. Hyōrinmaru's bankai, named Daiguren Hyōrinmaru (大紅蓮氷輪丸^?, literally "great crimson lotus ice ring"), causes ice to flow from Hyōrinmaru onto Hitsugaya, forming into two large wings, a tail, guards over his feet in the shape of dragon claws, and twelve large flower petals. During one of Hitsugaya's earlier battles, the arrancar Shawlong speculates that Hitsugaya's bankai will fade when all twelve petals disappear and that Hitsugaya's bankai is incomplete due to his young age. Later during his fight with Luppi, Hitsugaya states that "even if [Hyōrinmaru is] shattered, it will reform as long as there is water present.

Hyōrinmaru's bankai has four known special techniques. The first is Ryūsenka (竜霰花^?, literally "dragon hail flower"), which freezes any enemy Hitsugaya stabs, locking them into a cocoon of ice and freezing them to the core. Once frozen, Hitsugaya can shatter his opponent. The second is Sennen Hyōrō (千年氷牢^?, literally "thousand-year ice prison"), which forms a multitude of ice pillars using the moisture in the atmosphere. These pillars hold the enemy prisoner for a thousand years, also freezing them. His third technique, Guncho Tsurara (literally "icicle flock"), he launches a multitude of ice shards in an attempt to impale his opponent. His fourth, and implied most powerful move is called Hyoten Hyakkaso (literally "frozen sky-hundred flowers funeral"). This attack causes 100 snow flakes to fall from the sky, freezing anything they touch in a flower like shape. When all 100 flakes fall, the life of the one trapped by the attack is over.

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Sōsuke Aizen (藍染 惣右介 Aizen Sōsuke^?) is the captain of the 5th Division when first introduced, but then he betrays Soul Society and becomes the main antagonist of the series. His former lieutenant is Momo Hinamori. Aizen is a soft-spoken intellectual, accented by glasses during his time as a Soul Reaper captain. While he appears to be very kind to his subordinates, he cares very little for them in truth. According to Aizen himself, he is not bound by morals and will therefore stop at nothing to further his ambitions, including manipulating or killing anyone if he deems it necessary. Aizen is an extremely potent combatant, well above most captain-level Soul Reapers. He goes on to state that the only way for him to advance beyond that would be to gain and master hollow powers. His mastery of the regular skills are such that he is able to stop fully released zanpakutō, includingIchigo Kurosaki's bankai, with one finger, and he can defeat several captain-level opponents at once. A hint to his actual level of spirit power is given when he turns Wonderweiss Margera into an arrancar. When preparing to activate the Hōgyoku, he states that despite its half-awakened state, it can be fully activated when temporarily fusing with someone with twice as much spirit power as a captain-level Soul Reaper, referring to himself. The force of Aizen's spiritual pressure is also great enough to bring the 6th Espada, Grimmjow Jeagerjaques, to his knees without any visible effort from Aizen himself.

Aizen's zanpakutō is Kyōka Suigetsu (鏡花水月^?, literally "mirror flower water moon"). In its sealed form, it looks like a normal katana. Its shikai is both activated and deactivated with the command "shatter" (砕けろ kudakero^?). The phrase kyōka suigetsu suggests its illusory properties; the moon reflected in water and a flower in a mirror are things that can be seen but not held. It is a Chinese idiom for seeing and desiring something that is a dream that cannot be easily grasped in hand, teaching people about temptations.

Kyōka Suigetsu's shikai has the ability to place anyone who sees it under a state of "Perfect Hypnosis" (完全催眠 kanzen saimin^?), after which Aizen can make them see, hear, and feel whatever he wants. According to Aizen, the hypnosis is unbreakable, even if the target is aware that they are hypnotized. The only way to avoid the effect is to not see Kyōka Suigetsu's shikai, making the blind Kaname Tōsen immune to its effects. The effect seems to be permanent, or at the very least long-lasting, as Aizen uses it on nearly all of the lieutenants and captains in the Gotei 13 during a ceremonial release of his zanpakutō years before faking his own death. While the illusions Kyōka Suigetsu creates are quite powerful, they are not 100% accurate; Captain Retsu Unohana was able to realize that something was amiss with Aizen's fake corpse, even though she did not realize what until seeing Aizen alive.

Kyōka Suigetsu's hypnotic abilities make it a useful tool in combat as well, as Aizen can quickly create simple illusions to deceive opponents. By creating a decoy of himself, Aizen can hide his own movements and attack with impunity; his opponent, meanwhile, will remain focused on the illusion until it's too late to react. The most prominent example of this is his brief fight against Sajin Komamura, where an illusionary copy of Aizen is seen melting away after the real Aizen has moved close enough to use the devastating Black Coffin kido.

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