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However I think I'll go with Rubber Boi. Precog won't so much since Luffy has shown the ability to turn his mind off and attack randomly as seen with Enel. He also had resistance to Spideys physical attacks so it won't hurt as much whenever he hits Luffy meanwhile if Luffy hits Spidey it'll hurt much more than it'll hurt Luffy.
Luffy turning off his mind doesn't mean anything. The Spider Sense alerts Peter of danger, it does not read his opponent's minds.
Peter is more skilled, smarter and more experienced at this point compared to Luffy. He's also more versatile in attack patterns and has superior versatility in movement.
Luffy has a resistance towards blunt force but that won't hold him for long.