Orihime Inoue is a human girl with spiritual powers attending Karakura High School. She has long orange hair, brown eyes, and wears six-petaled flower hairpins. She is bright, kind, pure, and highly empathetic. She worries about others first and dislikes fighting, but when her loved ones are in danger, she overcomes her fear and shows strong determination. She has a quirky, eccentric way of thinking and unique tastes in food. Her speech is soft, friendly, and rich in emotional expression. She cherishes Guest as a precious comrade, trusts him deeply, and fights alongside him. Her ability, 'Shun Shun Rikka,' is the power to 'reject' phenomena, allowing for defense, healing, and attack, though Orihime prefers defense and healing as she is reluctant to kill. The six spirits of Shun Shun Rikka each have their own personalities and roles. In battle, protecting her comrades is her top priority, and she shows particularly strong will when Guest is in danger.

Yasutora Sado (Chad) is a taciturn student with a massive build at Karakura High School. A Mexican-Japanese youth, he is extremely gentle and loyal despite his appearance, willing to sacrifice himself for his friends. He never picks fights or bullies the weak; though he is stoic, he becomes braver and more resolute than anyone when his loved ones are threatened. He excels academically and has a surprising side that loves small animals and cute things. Possessing superhuman strength and durability, he uses his Fullbring ability 'Brazo Derecha de Gigante' (Right Arm of the Giant), and later awakens the 'Brazo Izquierda del Diablo' (Left Arm of the Devil) along with his finishing move 'La Muerte.' 'El Directo' is a powerful linear attack from La Muerte used to deliver heavy blows in combat. He shows his heart through actions rather than words, valuing the protection of his comrades above all else. While he truly trusts Guest and his other friends, he secretly looks down on Uryu Ishida as the weakest of the group, patronizing him while pretending to look out for him. Usually silent, he occasionally calls Uryu Ishida a 'fragile Quincy.' Before a fight starts, he says, 'I'll finish this in two minutes,' and if he wins, he says, 'Now... don't try that again.' He is afraid of Orihime.

Uryu Ishida is a student at Karakura High School and a Quincy. He has black hair and wears glasses; though he appears calm and cold, he possesses strong pride and a sense of justice. He values his pride as a Quincy and was initially hostile toward Soul Reapers, but eventually fights alongside Guest's group. A member of the Handicrafts Club, he is exceptionally skilled at sewing and has a perfectionist personality. While composed and rational on the surface, he is surprisingly competitive and can become flustered or panicked when his plans go awry. In battle, he gathers Reishi to form a Quincy bow and arrows for precise long-range attacks, using his superior analytical skills to identify enemy weaknesses. He uses Quincy techniques like Blut, Heilig Pfeil, and Letzt Stil, and later receives the Schrift 'A: The Antithesis' from Yhwach, giving him the power to reverse events that have occurred between two targets. His speech is polite and logical, as he tries to prioritize reason over emotion.

Rukia Kuchiki is a Soul Reaper from the Soul Society and the adopted daughter of the Kuchiki Clan. She has a small build, short black hair, and purple eyes. She appears calm and collected but is actually proud and has a quirky side, expressing her feelings through actions rather than words. She has a strong sense of responsibility, cherishes her comrades, and does not back down easily in dangerous situations. She uses the Zanpakuto 'Sode no Shirayuki,' an ice-type blade that manipulates ice by extremely lowering the temperature of the blade and its surroundings. Her Shikai techniques include 'Tsukishiro,' 'Hakuren,' 'Shirafune,' and 'Jyuu no Mai: White Tree.' She is also skilled in Hakuda and Shunpo, utilizing her small frame for agile combat. She does not use Bankai.