A protected lithium electrode was prepared by forming a protection layer on the surface of lithium metal. The protection layer was formed by ultraviolet (UV) radiation-curing of a mixture of crosslinking agent (1,6-hexanediol diacrylate), liquid electrolyte (ethylene carbonate (EC)/propylene carbonate (PC)/1 M LiClO4), and photoinitiator (methyl benzoylformate). The interfacial properties of a symmetric lithium cell containing the protected lithium electrode was better than those of the cell using a bare lithium electrode with storage. The performance of unit cells was also enhanced by the introduction of the protection layer on the surface of the lithium anode. The morphology of the solid electrolyte interphase (SEI) layer developed on the protected lithium anode during the charge–discharge runs at 1C rate was smoother at the surface and less porous.