A surface coating that simultaneously suppressed Li dendrite growth and polysulfide shuttling on a lithium anode was successfully developed using a polymer blend composed of Nafion® and polyvinylidene difluoride (PVDF). This hierarchically nanostructured composite coating efficiently alleviated the swelling and dissolution problems of cation-selective Nafion® in the electrolyte and provided sufficient mechanical strength to accommodate large volumetric variations in the Li anode during charge-discharge cycles. The Nafion®/PVDF-coated Li anode exhibited substantially enhanced rate performance and cyclability as well as improved Coulombic efficiency for Li-S prototype batteries with a high-S-content cathode.