Perform the following actions to unlock more characters.

Character	How to unlock
Baraggan Luisenbarn/No.2nd Espada	Resurrection Second Stage/Unlock in Story Mode.
Byakuya Kuchiki/Bankai	Unlock in Story Mode.
Coyote Starrk/No.1st Espada	Resurrection Second Stage/Unlock in Story Mode.
Grimmjow Jaegerjaquez/No. 6 Espada	Resurrection Second Stage/Unlock in Story Mode.
Ichigo Kurosaki/Bankai	Unlocked from the start.
Ichigo Kurosaki/Final Tensa Zangetsu Bankai Form )	Unlock in Story Mode.
Ichigo Kurosaki/Hollowfied )	Unlock in Story Mode.
Ichimaru Gin	Unlock in Story Mode.
Kenpachi Zaraki/Shikai )	Unlock in Story Mode.
Kokuto the Bleach Movie 4 villain	Mission Mode.
Nnoitra Gilga/No.5th Espada	Resurrection Second Stage/Unlock in Story Mode.
Rukia Kuchiki/Shikai	Unlock in Story Mode.
Shunsui Kyoraku/Shikai	Unlock in Story Mode.
Soi Fon/Shikai	Unlock in Story Mode.
Sosuke Aizen/Long Hair Chrysalis Form	Unlock in Story Mode.
Tia Harribel/No.3rd Espada	Resurrection Second Stage/Unlock in Story Mode.
Toshiro Hitsugaya/Banka	Unlock in Story Mode.
Ulquiorra Cifer/No.4th Espada	Resurrection Second Stage/Unlock in Story Mode.
Uryu Ishida/Hueco Mundo Arc Appearance	Unlock in Story Mode.
Yoruichi Shihoin/Anti-Hierror Armor	Unlock in Story Mode.