Jill of the Jungle is the oldest one I know of that isn't Metroid. Fairly certain Metroid was first, but everybody knows Samus. Nobody, even people my age, ever talks about Jill of the Jungle tho.
Playing Jill of the Jungle (and many other retro gems) on my grandpas computer when visiting is one of my core memories from my childhood. He had so many great games from that era that have since gone forgetten. I wish i could remember them all.