Falco
clear 100-man melee
play 300 VS matches

Ganondorf
clear event match 29
play 600 VS matches

Pichu
clear event match 37
play 200 VS matches
clear classic with Mewtwo

Luigi
clear adventure stage1 when the clock reaches xx:x2:xx and finish adventure mode
play 800 VS matches

Dr Mario
clear classic with Mario without continuing
play 100 VS matches

Jigglypuff
clear classic or adventure with any character on any difficulty
play 50 VS matches

Marth
clear classic with the 14 original characters
play 400 VS matches
use the 14 original characters in VS mode at least once

Roy
clear classic with Marth without continuing
play 900 VS matches

Young Link
clear classic with 10 different characters (two of them have to be Link and Zelda)
play 500 VS matches

Mewtwo
play VS mode for 20 hr
play 700 VS matches

Mr Game & Watch
clear classic with all 24 characters except him
play 1000 VS matches
clear target test with all 24 characters except him