My roommate has a cat who requires two boxes, one of which is for peeing and the other is for poo. He will not do his business in just one box. I think he is a bit of a weirdo, but hey you have to do what works. Also if the litter box is too near the food bowl she may be adverse to using it for that reason.
My cat scratches up the furniture and I am trying this new thing called Comfort Zone Spray. I have tried double sided tape, bitter apple spray, scratching posts, etc. and he still insists on scratching the furniture. Apparently this spray that I bought the other day uses a kitty phermone that they exert from their facial glands when they are comfortable and happy, and the cause of a lot of peeing/scratching in places where they shouldn’t is due to stress or discomfort about something. So far it appears to be working okay and that makes me really happy. They make it in a spray and a plug in that exudes this phermone all the time if they seem to be uncomfortable in one particular room.
I second (third or forth?) the suggestion of an additional box. According to my vet, the guideline is n+1 litterboxes (where n = the number of cats in the house). Which is why we have four litter boxes for our three cats - and yes, we were having pee incidents when we only had three boxes.
And use tons of the urine eliminator stuff when you’re cleaning the couch, including when you launder the covers. (They make a powdered version for use in the washing machine.) Regular laundry soap and water won’t remove all of it, and as long as she can smell any at all she’ll keep peeing there.
I’ve used the Comfort Zone plug, and it does solve a lot of behavorial problems. It’s really expensive though, so I wouldn’t recommend it as a permanent solution.
My cat went through a phase where he was peeing everywhere, and placing dishes of food in every room (sometimes in every corner of a room) is what finally broke him of it. It took a month or so for him to stop, but now he’s a litterbox only cat.
So to summarize:
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Get an extra litter box and scoop daily.
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It might also help to try a different type of box or litter but avoid highly scented litters and the crystals. Studies have shown cats don’t like it.
Some cats don’t like enclosed boxes, some might want a larger box. If you can’t find a box large enough get a nice-sized storage container and cut an entrance hole in it. -
Thoroughly clean the peed area with an enzymatic cleaner
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Put a food dish on the pee spot.
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Cover the area in plastic to prevent further soak ins of any new pee.
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Get a pheromone spray, like Feliway and spray around that spot.
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Get something to deter the kitty from even getting on the couch, such as a scat mat, aluminum foil, double-sided sticky tape or those little nubbly matts that are supposed to keep cats out of plants or off things. They don’t hurt, cats just don’t like the way they feel.
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Make sure there isn’t a new neighborhood cat hanging around outside that is literally pissing her off.
Thanks for all the suggestions, folks. Update: the Evil Pee has struck again. 
We moved the litterbox around the corner. No dice. Though it did have a fresh deposit of solids in it this morning, so I know she’s willing to use it. ArRRggh.
Ye. Flipping. Gods.
I mean, I thought cats were low-maintenance pets! She’s never been the needy type before…
I’ll look at picking up a new litterbox after payday. I dunno where I’m going to put it, mind, but we’ll figure something out I guess. Is the cat going to be happy with two litterboxes side by side, or do they need to be totally separated? I’ve never heard of multiple-box cats before. sigh
I tried Feliway once and it didn’t seem to do any good, but we’ll give it another go.
Thanks again for the suggestions, folks!
Ours are perfectly fine with all four sitting right next to each other in a corner of the basement.
Just keep in mind, once you have this problem licked she’ll go back to being low maintenance! 