E-DUB wrote:

The old "Spiderman" series was pretty good for that. One episode had William Smithers and Andrew Robinson. (Merrick and Garak!)
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If you mean the '70s
The Amazing Spider-Man series with Nicholas Hammond, it featured Michael Pataki (Korax) in a recurring role as a police captain. And Rosalind Chao (Keiko) had a featured role in the final 2-part episode. Other Trek guests in that show include Theodore Bikel, Barbara Luna, Paul Carr, Nicolas Coster, and Hagan Beggs. (Its guests also included some actors with other superhero connections -- JoAnna Cameron, aka
Isis; Gavan O'Herlihy from
Superman III; and Bob Hastings and Lloyd Bochner, who were Commissioner Gordon and Mayor Hill in
Batman: The Animated Series.)