The protection layer was introduced to the surface of the Li anode to enhance the charge/discharge performance of lithium/sulfur batteries. The protection layer was formed by a cross-linking reaction of the curable monomer in the presence of liquid electrolyte and a photoinitiator. When the Li anode is coated with the protection layer, the unit cells with a liquid electrolyte showed an enhanced charge/discharge performance as compared to cells based on a polymer electrolyte, resulting in an average discharge capacity of 270 mAh/g-cathode during 100 cycles. All the charge/discharge tests were performed at room temperatures.