Bowser Jr.
Play 100 Smash matches or beat Classic Mode on Normal difficulty as Bowser

Dark Pit
Play 50 Smash matches or beat Classic Mode on 5.0 difficulty

Dr. Mario
Play 60 Smash matches or beat Classic Mode on Normal difficulty as Mario

Duck Hunt
Play 110 Smash matches or beat Classic Mode on Normal difficulty as Luigi

Falco
Play 20 Smash matches or beat Classic Mode 1 time

Ganondorf
Play 80 Smash matches or beat Classic Mode on Normal difficulty with Link

Jigglypuff
Play 120 Smash matches

Lucina
Play 40 Smash matches or beat Classic Mode on Normal difficulty with Marth or Robin

Mr. Game & Watch
Play 90 Smash matches

Ness
Play 10 Smash matches

R.O.B
Play 70 Smash matches

Wario
Play 30 Smash matches or beat 100 Man Battle