I thought about this as I read Superior Spider-Man which sadly will end soon, and mentioned this in passing in Anya Corazon's thread. We've seen a little bit of interaction between Otto Octavius (as Elliot Tolliver) and Reed Richards, and I would like to see them develop a (grudging?) respect for each other's scientific achievements. If they can overlook any personality issues, and if Otto keeps his current body and SSM identity, this would be an interesting dynamic to visit from time to time.
Everyone's familiar with the legendary bromance between Peter and Johnny. Then we have the maternal relationship between Sue and Anya, which I want writers to revisit. So that leaves out Ben. Who among the 616 Spider-People could he bond with. Miles? If so, how would it happen?
(I'm deliberately excluding a pairing between a specific Spider-Person and a specific substitute FF member that's being shipped for years. Focusing on the original FF here.)