In Bleach: Soul Resurreccion (aka Bleach: Soul Ignition) for the PS3, there are several characters you can unlock in the game. Most are unlocked simply by playing through Story Mode, but a few are unlocked in Mission Mode.
Barragan – Complete Episode 9 in Story Mode
Byakuya Kuchiki – Complete Episodes 8 through 10 in Story Mode
Final Ichigo Kurosaki – Complete Mission 23 in Mission Mode
Gin Ichimaru – Complete Episode 13 in Story Mode
Grimmjow – Complete Episode 3 in Story Mode
Halibel – Complete Episode 8 in Story Mode
Hollowfied Ichigo – Complete Episodes 6 and 7 in Story Mode
Kenpachi Zaraki – Complete Episodes 2 and 3 in Story Mode
Kokuto – Complete Mission 5 in Mission Mode
Nnoitra – Complete Episode 4 in Story Mode
Rukia Kuchiki – Complete Episodes 3 and 4 in Story Mode
Skullclad Ichigo Kurosaki – Complete Mission 20 in Mission Mode
Sosuke Aizen – Complete Story Mode
Stark – Complete Episode 10 in Story Mode
Ulquiorra – Complete Episodes 6 and 7 in Story Mode
Uryu Ishida – Complete Episode 1 in Story Mode
Yoruichi Shihoin – Complete Episode 11 in Story Mode
