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The following playable characters become unlocked when you have earned the corresponding amount of Experince points. You will earn 20 Experience points each day you survive. Wes and Maxwell can only be unlocked through playing Adventure mode.
Wendy:
Survive a total of 32 days (640 Exp).
Wickerbottom:
Survive a total of 64 days (1280 Exp).
Willow:
Survive a total of 8 days (160 Exp).
Wolfgang:
Survive a total of 16 days (320 Exp).
Woodie:
Survive a total of 80 days (1600 Exp).
WX-78:
Survive a total of 48 days (960 Exp).
Maxwell:
Complete Adventure mode.
Wes:
Find a rescue Wes in Adventure mode. Whether he spawns or not is random.