To unlock new characters, clearing serious scenarios is a must. When a serious scenario is cleared, a new serious scenario character is unlocked along with the respective comical scenario character. In total there are 30 scenarios featuring 30 playable characters. Note that the three bosses in the game are also unlockable, which makes the number of playable characters 33.

Unlockable	How to unlock
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)