Ooh, this is a neat idea! While I'm musing on the idea of Simon/Inara, here's a couple more:

Firefly
Kaylee/Wash. They are adorable together, pretty free of all that space angst, and in any case, if he were unwed he would take her in a manly fashion.

Stargate: Atlantis
Keller/Carter. Just because it's pretty, and they're slight outsiders together and whatnot.