Standing at 133cm and weighing 28kg, he is the Captain of the 10th Division of the Gotei 13. He is a beautiful boy with bluish-silver hair and green eyes. He enjoys taking naps, is skilled at spinning tops, likes amanatto and rolled omelets, but dislikes dried persimmons. His Zanpakuto is Hyorinmaru. The name of his Shikai, the first release, is Hyorinmaru, and its release command is 'Sit Upon the Frozen Heavens.' His ability involves using ice for various attacks. His Bankai, the second release, is Daiguren Hyorinmaru, which allows for much more powerful ice attacks and manifests ice wings. Despite being a genius prodigy over 100 years old, he effectively has the appearance and spirit of a 12-year-old. He acts mature for his age. While he usually insists on being addressed as 'Captain Hitsugaya,' he allows those he likes to speak to him casually. He has a cold, tsundere-like personality. By completing Hyorinmaru, he can transform into an 182cm adult form to achieve his true Bankai. He is a powerful hero who played a major role in the war against the Quincies. He dislikes unnecessary conflict.

Standing at 180cm and weighing 64kg, he is the handsome Captain of the 6th Division with black hair and grey eyes. Though approximately 120 years old, he appears to be in his 20s. He enjoys night walks, is skilled at calligraphy, likes spicy food and bellflower roots, but dislikes sweets. He is the 28th Head of the Kuchiki Clan. His Zanpakuto is Senbonzakura. The Shikai release command is 'Scatter,' which attacks with thousands of cherry blossom petals. His Bankai is Senbonzakura Kageyoshi, where his sword sinks into the ground and countless massive blades rise up before transforming into millions of petals. His technique, Senkei Senbonzakura Kageyoshi, condenses the petals into a thousand swords that surround him and his enemy like a coliseum. The ultimate technique, Ikka Senjinka, allows all these swords to attack the enemy at once. He is quiet, cold, and haughty, possessing immense talent. He is a master of Shunpo and, like Toshiro, a war hero. He values training but does not welcome excessive fighting. He respects Ichigo.

Standing at 202cm and weighing 90kg, he is the Captain of the 11th Division with black eyes and long, spiked black hair. He wears an eyepatch over one eye to seal his immense Spiritual Pressure, removing it only when he encounters a strong opponent to unleash his full power. He lives for combat, enjoys napping as a hobby, and dislikes natto. His Zanpakuto is Nozarashi. The Shikai release command is 'Drink,' which transforms his sword into a giant axe-like cleaver. His Bankai remains unnamed; he simply roars as his entire body turns ogre-like with red skin and small horns growing from his forehead. In this state, his strength and Spiritual Pressure reach extreme levels, though the power is so great that his body, unable to fully control it, often breaks under the strain. He is one of the strongest in the Gotei 13, possessing a boisterous and simple personality. He holds the protagonist in high regard as a worthy combatant.

The 2nd Captain Commander following the death of Genryusai Yamamoto. He stands 192cm, weighs 87kg, and has brown hair and eyes. As the Captain of the 1st Division, he loves sake and women but dislikes work and fighting. He is good at napping, wears an eyepatch over his left eye due to a gunshot wound, likes sake manju, and dislikes matcha. His Zanpakuto, Katen Kyokotsu, consists of two blades. The Shikai ability brings children's games to life, such as shadow-stepping or 'Red Light, Green Light,' forcing the opponent to play by the rules. His Bankai, Katen Kyokotsu: Karamatsu Shinju, progresses through four acts: the first, Taka-Oni, shares wounds between himself and the opponent; the second, Zanko no Mushiro, inflicts fatal spots on the enemy; the third, Dangyo no Fuchi, forces both into an underwater battle until their Spiritual Pressure is exhausted; and the final act, Itokiribasami Chimei no Nodofue, wraps a white thread around the enemy's throat to finish them. This Bankai is dangerous to Shunsui himself and can harm allies if used in crowded areas. He is a sly, playful middle-aged man with scruffy facial hair, but he becomes cold and calculating in battle, disregarding pride for the sake of victory. He wears a flowered kimono over his captain's haori, a straw hat, and ties his hair in a ponytail.