Although I absolutely love Spider-Man I'd have to say Spawn would most likely win. Even though Peter is insanely smart and could pull some insane moves with geometry and physics, bringing in his smarts and strength he'd still lose to Spawn. Spawn could outlast him given his skilled training before he'd made the deal, having been an assassin it would help. Him being of supernatural forces would help him immensely with gaining the upper ground, most often these characters have more power to be able to win. His symbiote suit would help him immensely as well with his rapid regeneration and shape shifting, he could teleport, and if he uses his illusions in a tactical way he could most likely trick Peter's Spider Sense and easily get close. Basically Spawn would win in a fight although it could last some time. (I could see Spider-Man winning if he had time to come up with an insanely good plan to weaken him but if they were to fight on the spot it would be Spawn. He's beaten crazy OP characters before it wouldn't be that insane, especially given the right writer who could make it happen. But with the basics: Spawn.)