other ways (most of them thanks to marioplanetoid.com):
captain falcon-------beat classic in 20 min.
falco----------------beat 100 man brawl
ganondorf-----------clear all classic mode stages with link or zelda on hard
jigglypuff------------beat classic mode not with ike or beat event 20
lucario--------------play through sse with meta knight or do 5 target tests
luigi-----------------beat classic mode on easy
marth---------------beat classic mode any difficulty or get him in the sse
mr. game & watch---beat classic mode with every character
ness----------------reflect 10 projectiles or get him in the sse
rob-----------------can only unlock by playing 160 vs. matches
snake---------------play 15 matches on shadow moses island
sonic----------------complete sse or beat classic mode with 10 characters
toon link-------------beat classic mode with link
wolf-----------------on stage Iseki when lowering to the pit go to second door
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