The Con
Defeat Boneyard (Team Phantom) in Class D Story mode to unlock him in Arcade mode.
Defeat Cinder and her team in Class A Story mode to unlock her in Arcade mode.
Successfully complete arcade mode to unlock Hardcase in Quick Play mode.
Defeat KFJ (Team Rogue) in Class B Story mode to unlock him in Arcade mode.
Successfully complete Arcade mode on the Hard difficulty setting with a Jeet Kune Do fighter to unlock Mask (Jeet Kune Do) in Quick Play mode.
Successfully complete Arcade mode on the Hard difficulty setting with a Kickboxer to unlock Mask (Kickboxing) in Quick Play mode.
Successfully complete Arcade mode on the Hard difficulty setting with a Street Boxer to unlock Mask (Street Boxing) in Quick Play mode.
Successfully complete Arcade mode on the Hard difficulty setting with a Tae Kwon Do fighter to unlock Mask (Tae Kwon Do) in Quick Play mode.
Successfully complete Arcade mode on the Hard difficulty setting with a Wrestler to unlock him in Quick Play mode.
Successfully complete Story mode to unlock Reina.
Defeat Shaman and his team in Class B to unlock him in Arcade mode.
Defeat Smoke and his team in Class C to unlock him in Arcade mode.
After unlocking a character in Quick Play mode, highlight the "Random" option at the character selection screen and press Circle until that character appears.
Defeat Cinder's (Class A), Shaman's (Class B), Smoke's (Class C), and Bonyard's (Class D) teams to unlock items used by the corresponding team leader.