| Unlockable: | How to Unlock: |
| Aizen Sousuke | Complete Part C 100% |
| Don Kanonji | Complete Part C 100% |
| Goteitaishi | Complete Story Mode A-D with 100% on any difficulty. |
| Grandfisher | Complete Story Mode A-D with 100% on any difficulty. |
| Ichimaru Gin | Complete Part B 100% |
| Iduru Kira | Beat him in the Story Mode, in a level where you face him and Rangiku. |
| Kukaku | Complete Part B 100% |
| Kyugohanin | Complete Story Mode A-D with 100% on any difficulty. |
| Menos-Grande | Complete Story Mode A-D with 100% on any difficulty. |
| Ogihci | Complete Part C 100% |
| Rangiku Matsumoto | Beat her in the Story Mode, in a level where you face her and Iduru. |
| Ririn | Complete Part C 100% |
| Rukia Kuchiki | Beat the first part of the Story Mode. |
| Shibata | Complete Story Mode A-D with 100% on any difficulty. |
| Shrieker | Complete Story Mode A-D with 100% on any difficulty. |
| Shuhei Hisagi | Beat him in the Story Mode. |
| Soifon | Beat her in the Story Mode. |
| Tatsuki | Complete Part C 100% |
| Tosen | Complete Part A 100% |
| Tsukaima | Complete Story Mode A-D with 100% on any difficulty. |
| Ururu | Complete Part A 100% |
| Yachiru Kusajishi | Beat her in the Story Mode. |
