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Waluigi: Play 5 hours of events in event mode.
Princess Daisy: Play on the Sarasaland stage as Luigi.
Luigi: Have Luigi join you in story mode.
Roy: Defeat Giant False Marth in story mode.
Koopalings: Play on all stages as Bowser and Bowser Jr..
Marth: Play on the Castle Siege stage as all characters.
Princess Elincia: Complete team mode as Lyn.
Lucas: Play on the Onett stage as Ness.
Amy Rose: Defeat Jet the Hedgehog in story mode.
Falco Lombardi: Play on the Lylat Cruise stage as Fox.
Toon Link: Clear all-star as Link without continues.
Wolf: Unlock Falco Lombardi.
Jin Kazama: Play on the Moonlit Wilderness stage as any character.
Paragoomba: Beat Paragoomba in story mode.
Baby Donkey Kong: Obtain 6 Donkey Kong trophies.
Captain Syrup: Beat Giant Captain Syrup in story mode.
Cranky Kong: Play on the Rainbow Road stage as Pauline.
Lucario: Beat Giant Pikachu in story mode with Mewtwo.
Mewtwo: Play on the Pokemon Stadium stage as Lucario.
Jigglypuff: Buy five or more recipes like spam or beef in Revenge Food Buying Money mode in vault.
Pauline: Play on the Rainbow Road stage as Diddy Kong.
Mr. L: Play as Luigi 3-4 times in a match.
Only 2 items are unlockable.
PokeBall: Defeat Pikachu in all-star mode.
Assist trophy: Beat Giant Assist Trophy in story mode.
Unlockable assist trophies
Only 1 assist trophy is unlockable.
Paula: Beat Paula in story mode.