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The simplest way is to defeat the Subspace Emissary. Oh, and about Toon Link, Jigglypuff, and Wolf, you have to go back to the Forest, Swamp, and the Ruins and find an extra door to defeat them. But then, you have to beat Tabuu, and the Great Maze. Good luck.

Oh, and there ARE other ways, but I'm afraid you have to Google it. I believe you have to play Brawl multiple times and defeat a character to win. I don't know. Good luck with Tabuu.

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Q: How do you unlock everyone on Super Smash Bros. brawl?
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