Vet first, to rule out medical problems. Try extra litter boxes. Mine also use one for #1 and one for #2 and 1 cat will only go on a smooth flat surface, with no litter. So I put down a large lid from a rubbermaid storage container, and she uses that...strange, but loveable creatures! They keep you guessing! Good luck.
This sounds like an easy fix, but we had a similar problem with our cat, which was an indoor cat. We were able to get to the spots easily, where she decided to poop, usually beside or near the litterbox! I scooped up some, put it in the litter box & she went right to the box, smelled her own scent and never had a problem again. I had cleaned the litterbox, washed and disinfected it and she needed to know it was actually hers I guess. Good Luck hope you get the problem solved.
Take him/her to the vet to see if they have a urinary tract infection, so that it can be treated. UTIs can be fatal in male cats.
I see a lot of posts in the archives about their cats doing #1 or #2 in the litterpan, but not the other. Try getting two litter pans. Seriously! I have 4 cats, and they are all indoor cats. I have 2 litter pans and they do #1 in one of 'em, and #2 in the other. Go figure.

Where is he going? I had a Maine Coon for 18 years that would never use a litter box. I always said he thought he was too good for one. =) He insisted on going outside to potty. We would leave him in the house for a whole weekend, every weekend, to go camping, and he would actually hold it the entire time. As soon as we came home, he almost knocked us down to get out.
I've had a lot of cats in my lifetime (have 4 now), but he was the only cat I have ever owned that simply refused to use a litter box, but yet never went in the house. As he and my dog became elderly, I would lay a "pee pee pad" down for my dog at night in case, like a lot of elderly, she might need to go during the night. She would use it often, and lo' and behold, my Maine Coon started doing the same thing! He would never use a litter pan, but as he got older, he would use the dog's "pee pee pad". Good luck to you!

Some questions come to mind:
Is this the only cat? Some won't share boxes.
Is it kept clean? Cats don't like dirty boxes.
Was this an outside cat that you're trying to convert? Some adult cats won't change.
Does the cat have a regular place it DOES use? You might need to cover that place, because cats like to go back to the same spot.
Just some stuff to think about.
I have a 4 year old male cat. He has decided that his litter box is used for #2 only. He has found it more comfortable to urinate on everything in the basement and under my bed instead of in his litter box. I have a laundry shoot and when the clothes hit the floor, if I don't get down there fast enough, he has already urinated on them. I have more ruined clothes than anything. I need to know what can I use to get the urine smell out of my house? What can I do to keep him for doing this in the future. Jessica from Roseville, MI
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My cat had a litter of four cats about 4 years ago. Three of the cats are litter box trained - one is not. This one cat has never used a litter box. I have tried everything from getting her her own box to putting her in a separate area with a box.
She used to use a rug that was next to the other litter boxes and she did very well with that for a while. We have recently moved and she will only go to the front door of all places. We are having the carpet replaced in our new home because we cannot get her house broken or to even use a rug now. Any suggestions?
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A boyfriend once called my cat a "dirty, hairy little slut" and she stalked out of the room in great indignation as he apologized to her: "I was only teasing, Tattoo." When he went into the bedroom where he'd left his overnight bag, there was a little present next to it. (04/24/2008)
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