Wyatt Wingfoot and Johnny Storm
Wyatt Wingfoot and Johnny Storm
Deathstoke and Wintergreen (well, except for that whole 'severed head' thing)
I always liked the Michael Holt (Mr. Terrific) and Pieter Cross (Dr. Mid-Nite) relationship in JSA, but then they kind of pushed it aside, and it became like it was never a thing.
But IT WAS A THING!!!!
EDIT -- Apologies! I see that this thread is supposed to be about friendships between heroes and non-heroes, not heroes and heroes. However, I still think the above is true, and I'm not taking it down.
As to hero and non-heroes friendships, the most famous one was Superman and Jimmy Olsen. That engendered a lot of hilarious stories, but somehow I never took to it.
Sandy Hausler
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I would choose Conner (Superboy) with Tana,Roxy,Dubbilex,Simon,Luthors Niece.......
Reading the Superbaby stories in the old SUPERBOY comics, I would say Superbaby with baby Lana (also with baby Lex and baby Pete Ross).