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The following characters become available when you complete the corresponding task. There are 30 scenarios featuring 30 playable characters. The three bosses in the game are also unlockable.
Asbel(TOG Comical):
Clear Cheria's story(after Rid's).
Chester(TOP Comical) and Yuri(TOV Serious):
Clear Cless's story (playable from the beginning).
Duke(Boss):
Clear a tournament in hard mode without retrying.
Elraine(Boss):
Clear ALL 30 stories.
Farah(TOE Comical) and Cheria(TOG Serious):
Clear Rid's story(after Chloe's).
Flynn(TOV Comical) and Emil(TOSR Serious):
Clear Yuri's story(after Cless's).
Kohak(TOH Comical):
Clear Shing's story(after Spada').
Leon(TOD Comical) and Guy(TOA Serious):
Clear Stan's story (playable from the beginning).
Luca(TOI Comical) and Shing(TOH Serious):
Clear Spada's story(after Jude's).
Luke(TOA Comical) and Kyle(TOD2 Serious):
Clear Guy's story(after Stan's).
Marta(TOSR Comical):
Clear Emil's story(after Yuri's).
Milla(TOX Comical) and Spada(TOI Serious):
Clear Jude's story (playable from the beginning).
Reala(TOD2 Comical):
Clear Kyle's story(after Guy's).
Rubia(TOT Comical):
Clear Caius's story(after Lolyd's).
Schwartz(Boss):
Clear ALL freemode challenges with gold medals rewarded.
Senel(TOL Comical) and Rid(TOE Serious):
Clear Chloe's story (playable from the beginning).
Tytree(TOR Comical) and Lolyd(TOS Serious):
Clear Veigue's story (playable from the beginning).
Zelos(TOS Comical) and Caius(TOT Serious):
Clear Lolyd's story(after Veigue's).