Lithium–oxygen batteries are of great interest because of their very high-energy density; however, they present many challenges, one of which is the low cycling stability of a lithium (Li) metal anode. Here, we report a composite protective layer (CPL) comprising Al2O3 and polyvinylidene fluoride-hexafluoro propylene for a Li metal anode that resulted in a dramatic enhancement of the cycling stability of a lithium–oxygen battery. A cell with the CPL-coated Li metal anode exhibited more than 3 times higher discharge capacity at the 80th cycle compared to a cell without the CPL. X-ray photoelectron spectroscopy measurements for the cycled lithium metal anodes confirm that the CPL effectively suppressed electrolyte decomposition at the surface of the Li metal anode.