1) Make an appointment with your vet to rule out a medical problem like a Urinary Tract Infection (URI).
2) Like Karen said, buy an enzyme cleaner to help clean up the pee area so he won't want to go there again. I've been using Simple Solution which you can buy at most pet stores.
3) Make sure that his litter box is very clean and you may also need to try an unscented litter. I'd recommend Cat Attract by Dr. Elsey which will help cats to start using their litter boxes again. It also comes with a booklet inside that tells you more about solving litter box problems.
4) You can also try buying some Feliway/Comfort Zone in a spray and after you clean up the area with an enzyme solution then spray it with Feliway to help prevent him from wanting to pee here again. You can also buy the plugins to help keep him calm and will hopefully prevent this problem 24/7.
5) If he only has one litter box then please buy him at least 1-2 more. The rule of thumb is to have at least one more litter box than you do cats.
6) I'm assuming that he's already neutered but if he isn't then you need to get him fixed asap.
I know that this is frustrating but hopefully some if not all of these things mentioned above will help you to solve his problem. Good luck.
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