Klingons,Romulans.
Klingons, Romulans, Talosians, ?The Borg? (the Planet Killer was supposedly a weapon built to destroy the Borg - non-canon source), Tribbles.
The Borg didn't appear until The Next Generation and the Planet Killer was just a rogue doomsday weapon from a war where both sides had been destroyed (nothing to do with the borg)
But these did appear
The Gorn, Tholians, Mudd, Kahn (then again in Star Trek 2),
Evil Kirk (Enemy Within) Trelane (a Q type entity).