Although “vs.” isn’t part of the movie title, I think “The One” deserves an honorable mention because the whole movie was about Jet Li’s character facing off against many other versions of himself in parallel universes. It came down to the good Jet Li, “Gabe”, vs. the ultimate villainous alter ego of himself, “Lawless”.
1958 – Earth vs The Spider
The title was shortened to, “The Spider,” for some reason.
2001 – Earth vs The Spider
TVM featuring Dan Aykroyd and John Cho. Rip-off of Spider Man.
and there’s the original Shark vs. Octopus. Stills from this appeared in the Wonders of Science book I had as a kid, and it was spliced into Ray Harryhausen’s first solo film, The Beast from 20,000 Fathoms. One commenter noted that it showed up in the first Flash Gordon serial, too