Complete the following tasks to unlock the corresponding character.

Unlock S. G. Yamamato:
Either complete 'Yamamato's Cooperation' In Free Time mode or defeat him in Bleach Tower, Level 4.

Unlock Yoruichi Shihouin (Current):
Either complete 'Yoruichi's Cooperation' in Free Time mode or defeat her in Bleach Tower, Level 5.

Unlock Shaolin Fong (Soi Fon):
Either complete 'Soi fon's Cooperation' in Free Time mode or defeat her in Bleach Tower, Level 5.

Unlock Gin Ichimaru:
Defeat him in 5 turns (before Izuru) in Bleach Tower, Level 6.

Unlock Izuru Kira:
Either complete 'Izuru's Cooperation' in Free Time mode or defeat him in Bleach Tower, Level 6.

Unlock Retsu Unohana:
Either complete 'Unohana's Cooperation' In Free Time mode or defeat her in Bleach Tower, Level 7.

Unlock Hanatarou Yamada:
Either complete 'Hanatarou's Cooperation' in Free Time mode or defeat him in Bleach Tower, Level 7.

Unlock Hinamori Momo:
Either complete 'Hinamori's Cooperation' in Free Time mode or defeat her in Bleach Tower, Level 8.

Unlock Byakuya Kuchiki:
Either complete 'Byakuya's Cooperation' in Free Time mode or defeat him in Bleach tower, Level 9.

Unlock Renji Abarai:
Either complete 'Renji's Cooperation' in Free Time mode or defeat him in Bleach Tower, Level 9.

Unlock Kaname Tousen:
Defeat him in Bleach Tower, Level 12.

Unlock Sajin Komamura:
Either complete 'Komamura's Cooperation' In Free Time mode or defeat him in Bleach Tower, Level 10.

Unlock Shunsui Kyoraku:
Either complete 'Kyoraku's Cooperation' in Free Time mode or defeat him in Bleach Tower, Level 11.

Unlock Shuuhei Hisagi:
Either complete 'Hisagi's Cooperation' in Free Time mode or defeat him in Bleach Tower, Level 12.

Unlock Yoruichi Shihouin (Former):
Defeat her in Bleach Tower, in the level she is in with Kisuke Urahara.