I think I knew the answer to this right from the start, but I had long enough for other possibilities to start elbowing in. I considered Ryoko and Tenchi, but I never saw them actually become a couple. Tommy Monaghan and Deborah Tiegel - that's "Tiegel" to you - gained a lot of traction. With those two I always think of the scene as they try to hold off the Mawzir's forces from inside the church. Tommy with a big shit-eating grin, asking, "C'mon, am I really such a bad guy?" and Tiegel responding "YES!" as some poor sap is getting launched through the background by an explosion. Unfortunately, I couldn't get a decent shot of it, so here's an extremely awkward moment instead.
Even so, the choice is Peter Parker and Mary Jane Watson-Parker.
Jeez MJ, it's supposed to be a happy occasion.
When I first started reading comics, MJ and Peter weren't a couple. They were friends, probably the closest friends either had, but they weren't dating. MJ knew Peter was Spider-Man - had known for years - and now Peter knew that. MJ had understandable reservations, but she was still his friend. She helped him repaint his apartment after some punks torched it, and had even offered to let him stay with her. By the next time I got some comics, they were married, which seemed perfectly normal to me. They were friends, then they fell in love and got hitched. Made sense to me.
I think they're a good couple. They argue, but they make up. They don't forget they love each other. They each will try to deal with things by themselves, to spare the other, but ultimately they share the load. And they were clearly attracted to each other. In the comics of my youth, those two were making out at the drop of a hat. This probably formed my impressions of marriage, but the couple finding each other attractive and acting on it, and this being presented as perfectly OK seemed fine to me.
Tiegel opts for an interesting opening move in some issue of Hitman. I'm going to guess Garth Ennis (writer), John McCrea (penciler), Garry Leach (inker), Carla Feeny and Heroic Age (colors), and Willie Schubert (letterer). Mary Jane can't believe how bad her favorite TV show's gotten, and Peter gets a pretty good welcome for being away for two weeks without a word in Web of Spider-Man #32, by J.M. DeMatteis (writer), Mike Zeck (pencils), Bob McLeod (inker), Jason Tetrault (colorist), Rick Parker (letterer). Pete's reminded he can't slip bullshit past MJ in Spider-Girl #44, by Tom DeFalco (script and plot), Pat Olliffe (plot and pencils), Al Williamson (inker), Christie Scheele and Heroic Age (colorists), John E. Workman (letterer). Mary Jane has good news for Peter, which means they're doomed in Amazing Spider-Man #398 by DeMatteis (writer), Bagley (penciler), Larry Mahlstedt (inker), Bob Sharen (colorist), and Bill Oakley (letterer). The likely moment when the bundle of joy in the previous page was conceived in Amazing Spider-Man #381 by David Micheline (writer), Mark Bagley (penciler), Emberlin and Milgrom (finishes), Rick Parker (letterer), and Bob Sharen (colorist).