What are all the ways to unlock characters in super smash bros melee?

Answer 1

Jigglypuff:

Play classic mode for the first time.

Luigi:

On adventure mode in the Mushroom Kingdom cross the finish line when the seconds counter has a two in it [Example] 3:42:54.

Dr.Mario:

Play classic mode as Mario.

Marth:

Play Vs. mode with all starter characters at least once.

Ganondorf:

Clear event match 29.

Falco:

Clear 100-man melee.

Pichu:

Clear event match 37.

Roy:

Play classic mode with Marth without continuing.

Young Link:

Play classic mode with ten characters (Two have to be Link and Zelda).

Mewtwo:

Play one Vs. match for twenty hours (leave the console on for twenty hours in a Vs.match)

Mr.Game and Watch:

Clear Target Test with all other characters.

Also

Jigglypuff50 vs. matchesDr. Mario100 vs. matchesPichu200 vs. matchesFalco300 vs. matchesMarth400 vs. matchesYoung Link500 vs. matchesGanondorf600 vs. matchesMewtwo700 vs. matchesLuigi800 vs. matchesRoy900 vs. matchesMr. Game & Watch1,000 vs. matches

Answer 2

jigglypuff,dr.mario,falco,gannondorf,young link,marth,roy,pichu,mewtwo,luigi and mr. game and watch