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When you complete the indicated Story mode the corresponding character will become available.
Unlock Izumi:
Complete Roy Mustang's or Riza Hawkeye's Story mode.
Unlock Riza Hawkeye:
Complete Edward Elric or Alphonse Elric's Story mode.
Unlock Roy Mustang:
Complete Edward Elric or Alphonse Elric's Story mode.
Unlock Scar:
Complete Roy Mustang's or Riza Hawkeye's Story mode.