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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