Drain peaches, reserving 1 cup liquid. Set aside.
Place ham slice in a 12- x 8- x 2-inch baking dish. Pour peach liquid over ham; sprinkle with sugar. Insert cloves in ham. Bake, uncovered, at 300° for 45 minutes. Place reserved peaches around ham; bake 15 minutes or until peaches are heated. Serve peaches with ham.