Ooooh, Mulder/Scully. For all the reasons you and Cath mentioned. The closest second is Roslin/Adama, but they are a very distant second. If only because I feel like I LEARNED to ship with Mulder/Scully (though, like you, they were not my first ship). And honestly and truly, there is no couple I ever felt like..."y'know, when I grow up, I WANT that. Exactly that."

Hell, I didn't even know what the word "shipping" meant until Mulder/Scully. (In fact, I'm pretty damn sure XF fandom coined that specific phrase, even though there were certainly other fandoms before it that participated in ship activities.)

(It's Alyssa. I don't want to sign up for an LJ account, hee.)