Birdo is a pink Yoshi-ish egg-spitting boss in SMB 2. Originally, Birdo was a boy who thinks he's a girl, but Birdo's just female now.
Waruigi's first appearance is Mario Tennis on the N64. He's the same relation to Luigi as Wario is to Mario: evil twin (or possibly longlost cousin). He looks like luigi in purple overalls and with a Wario-like nose and moustache.
Geno is the a messenger from the Star Road in Super Mario RPG. He's a spirit who possesses a little boys doll, named Geno. Geno looks like Pinnochio.
Wart is a big fat toad (not a _Toad_, just an ordinary toad) who takes control of Subcon, the land of dreams in SMB2. Not a whole lot unlike Bowser, Wart spits bubbles instead of fireballs.
Anyone else?