
Abarai Renji. Lieutenant of the 6th Division Squad. He is Rukia's childhood friend before enrolling as a Death God in Seireitei. He was placed in charge of bringing back Rukia from the human world and to exterminate Ichigo. This is because Soul Society finds it unacceptable to lend Death God powers to anyone in the human world without consent. Deep inside, Renji was frustrated when he knew Rukia was sentenced to execution for her crime, and blames it on Ichigo. When Ichigo arrived in Seireitei, Renji took the opportunity to settle scores with Ichigo and battles it out with him. Renji possesses the power of Zabimaru, which is the name of his flexible and deadly Zanpakutou (Soul Slayer Sword).

Shihouin Yoruichi. Former Head of the Correction Corps and 2nd Divison Squad. As swift and agile as she always been, Yoruichi was nicknamed as the "God Of Flash". Born into the noble Shihouin family, she is smart, sarcastic, and extremely confident. She does not hesitate to show off her impressive talents at the same time being well aware of her limitations.. She has mastered Flash Step, and is possibly the most talented practitioner in history. These combine to make her a lethal opponent easily capable of taking on a captain-class enemy, even without a Soul Slayer. Yoruichi also has the ability to transform herself into a black cat, which she uses to accompany Urahara in the mortal world.

Kira Izuru. Lieutenant of the 3rd Division Squad. A thin and somewhat neurotic individual, Kira is a good friend of fellow Lieutenants Hinamori and Renji. He seems a decent enough sort, but is also extremely loyal to his captain. This sometimes puts him in difficult positions, where he is forced to choose between loyalty to his captain and loyalty to his friends. During the fight against the Bounto, Kira played a part in infiltrating the Bounto territory, using his Zanpakutou with the ability to double the weight of any object his Zanpakutou cuts.

Matsumoto Rangiku. Lieutenant of the 10th Division Squad. Matsumoto is actually quite a capable and loyal Vice-Captain. She has a good relationship with her Captain, who, despite his seeming annoyance at her sleeping on the couch during working hours, holds great respect and even admiration for her. Besides having some history with Gin, she also accompanied her Captain to the mortal world to join forces with Ichigo in the fight against the Arrancar. Always proud of her assets, Matsumoto never fails to gain the attention of men, especially in Karakura Town.

Ichimaru Gin. Captain of the 3rd Division Squad. He was the very first Captain that Ichigo encountered on entry to Seireitei. His Zanpakutou, named as Shinsou, looks like an ordinary average sword on appearance. However, upon activation of its powers, it is able to shoot a missile-like beam on the latter. Gin used to be Aizen's Lieutenant in the past, and now has proven himself capable to hold the rank of a Captain. Still, Gin holds loyalty to Aizen and being sly and cunning as he is, Gin seems to have other motives than leadings his squad to uphold the laws of Soul Society.

Hitsugaya Toushiro. Captain of the 10th Division Squad. Perhaps the youngest of all the Captains, or even all of Seireitei. With silver hair and a gullible look, Hitsugaya is but a boy genius who made it this far at such an age. He is known as a prodigy in studying shinigami arts, and he is capable of unleashing vast destructive powers of ice. Despite his youth, Hitsugaya is one of the more mature captains, level-headed and perceptive, if a bit lacking in the humour department. Aware of the many strange occurances in Soul Society, Hitsugaya, together with his Lieutenant Matsumoto, revolves around searching out the source of the problems, also lending support against the Bounto and the Arrancar.
Soi Fong. Captain of the 2nd Division Squad, Commander of Covert Operations and Executive Militia. A rather swift fighting Captain, with abilities that can match that of Yoruichi. She is from a lower noble that served the great Shihounin family, and became a comrade of Yoruichi at a young age. In combat, Soi Fong wields Suzumebachi, one of the more unique Zanpakutou, which normally inflicts poison-like attacks. She was also one who defends Seireitei faithfully against the Bounto, and apparently took on one of them by herself.