Lithium (Li) metal is an ideal anode candidate for rechargeable batteries because of its ultra-high theoretical specific capacity. Unfortunately, the practical application of Li metal anodes is severely limited by the uncontrollable formation and growth of dendrites and infinite volume expansion. Thus, a protective layer is essential for stable and high-performance Li metal anodes. In this work, we demonstrate an organic-inorganic hybrid interfacial protective layer on Li foil surface (pa-Li) consisting of the organic polyvinylidene fluoride-hexafluoropropylene copolymer（PVDF-HFP）and inorganic Ag-LixAgy composite species. Going beyond conventional protective layers, we demonstrate that our hybrid protective layer is flexible and enabled strong interfacial adherence due to an alloying process. Furthermore, owing to the protective layer’s outstanding lithiophilicity and mechanical stability, the pa-Li││pa-Li symmetric cell exhibits satisfactory stability and reversibility for 1000 h at 5 mA cm-2, 5 mA h cm-2 with a low voltage hysteresis of ~ 70 mV, while the full cell with a LiFePO4 cathode delivers an excellent reversible capacity of 128.9 mA h g-1 for 900 cycles at 2 C with a capacity decay rate of 0.009% per cycle. This work proposes a design protocol for synergistic effect of PVDF-HFP organic species and Ag-LixAgy inorganic species and provides a prospective way to practical application of highly efficient, long lifespan Li metal batteries.