My turn:
Pokemon Special: Giovanni/Sabrina.
Normally they don't interact at any format but the Special manga shows Rina having interest in the Boss Rocket (as an utterance too). And combined with their anime pasts, makes an interesting pairing.
Giovanni has issues with his mother who made him who he is and he has a double life: split into being the Viridian Gym Leader and Boss of Team Rocket. He's usually stuck being the Boss or the greatest Gym Leader rather than be just Giovanni.
Sabrina has high level psychic powers, doesn't show emotion in normal conversion (only in the battlefield) and the other Gym Leaders fear her for her powers and stoicism. That can create a schism as she would like to show herself but can't because of her feared image, like Giovanni. And like the Boss Rocket, she has issues with her father (she inherited her powers from him, which led to her outlook on things, with the disclipine and training). I double took when Rina admitted that in the manga since either one you don't see with anyone (maybe Gio and Domino but that's...offputting a little bit because of the Black Tulip's age.). Too bad it didn't pan out but that's why there is fanfiction.
Anime: I do like Ash/Misty and Jessie/James, but truthfully, it wouldn't matter if the show did it or not, that's what the fiction is for, although after Forest Grumps, made me appreciate Jessie/James considering their halted relationship until...sixth season. And the chemistry is palpable but end of the day, I'm more underground pairings.
Games: no one has much of personality, but the Rocket Executives. They're so passionate with Giovanni's return, I think the passion would spill into each other and have an idolism going on there (like the female to the male, as he seems to have the most rank). I'm not sure.
There you go, but I develop new pairings on the drop of a hat. So yeah, and lately, I like James/May.
I think it's because they're so neurotic.