Make a list of all the characters in your icons. (Although you may have more than one icon of a single character, they only go on the list once.) Alphabetize it. Take the first two people on the list; that's your first pairing. Second two people; second pairing. Etc.
Andrew Wells (Buffy) & Anya Jenkins (Buffy) - This would clearly actually be in a threesome with Xander. Otherwise, Andrew would be like, "Eww, female," and Anya would be like, "Can't we kill him yet, Buffy, please?"
Cordelia Chase (Buffy/Angel) & Dana Fairbanks (The L Word) - Hmm. Possible, I suppose. Cordelia would be all about getting Dana to be more stylish, and she'd certainly like the fact that Dana's famous; I'm not sure what Dana would think about Cordelia, but she certainly wouldn't be put off by Cordelia's latent rich-kid mannerisms given her background.
Dodo (Alice in Wonderland) & Faith (Buffy) - *snort* I think this must have stemmed from
here. No comments on the actual pairing.
Goombella (Paper Mario) & Harry Potter (Harry Potter) - *dies* In a way, Goombella is not unlike Hermione, so I suppose if someone ever makes Hogwarts 2D, then all the H/H shippers will be happy with this. Ian says he just pictures Harry getting head-bonked over and over.
Illyria/Fred Burkle (Angel) & Inara Serra (Firefly) - Oooooh. Since this is really Illyria and not Fred, the dynamic would be very interesting; but I imagine that Illyria might lure Inara in while in Fred-guise, and then shift back once they're already getting it on.
Kaylee Frye (Firefly) & Lara Perkins (The L Word) - Just. Too. Cute.
Lilah Morgan (Angel) & Lindsey McDonald (Angel) - This is clearly inevitable when you're a lawyer at Wolfram & Hart and are therefore automatically going to fall in the roster right next to all of your colleagues.
Oz Osbourne (Buffy) & River Tam (Firefly) - Wow. Monosyllables + practical stream-of-consciousness? Oz would be so sweet to River. Kind of like Simon... ;)
Rupert Giles (Buffy) & Tara Maclay (Buffy) - Nooooo. Not romantically. I never can deal with Giles together with any of the Scoobies. (ETA: In this particular case, I'm identifying the Scoobies as the core group of 3, plus Tara... Giles and Anya is fine.)
Willow Rosenberg (Buffy) & Xander Harris (Buffy) - Well, duh. At least until season 4. :)