Just curious, do y'all being a couple mean anything to the FAA?
If you're both being hired OTS right now, no. Ideally you'll have kids already or soon, so you can get divorced and then one of you can hardship to the other's location "to be with the kids" (and then you can get remarried again), because there's no other way you'll go to the same place.
If your spouse is already an FAA controller, they will attempt to get you a slot at their facility, probably subject to level rules (i.e. if it's a terminal fac, only level 7 and below). I don't know much about that though.