Well, Zoro has shown as great or greater feats of strength and speed. Observation haki cancels out spider-sense. Then it comes down to Zoro's swords vs Peter's webs and intellect. Zoro would just slice through any webbing, so I give it to Zoro.
Zoro. He's butter in all physical aspects by a fair margin and his observation haki can counter Spidey sense combined with his bladed close range combat and superior ranged combat since he can slice arc blasts of pure force. Yeah Zoro wins this really. He's about equal to Luffy, some would say he could even beat Luffy given his swords and superior stamina.
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