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You can also ask your question on our Puyo Puyo Tetris Questions & Answers page.
When you clear the indicated Chapter in Adventure mode the corresponding character in the other modes will become unlocked.
Draco-Centauros and Witch:
Clear Chapter 5.
Ecolo and X:
Clear Chapter 7.
Lemres and Satan:
Clear Chapter 6.
Schezo and Feli:
Clear Chapter 4.