Doomsday (Earth-38: Pre-Crisis)

"Superman, champion of Earth, who faced off with Doomsday, apprehended General Zod, and went toe-to-toe with dozens of Lex Luthor's death traps, has finally met his match. A dirty diaper."

- Lois Lane to Clark Kent

Doomsday was a supervillain who faced Superman.

Battling Superman
At some point, Doomsday fought Superman but eventually lost.