Lithium metal with high theoretical capacity (3860 mAh/g) and low operational voltage (−3.04 V vs. standard hydrogen electrode) reflects to be one of the most high energy density anodes for energy storage devices. While, its high chemical activity to continuously react with electrolytes causing low coulombic efficiency and formation of lithium dendrites leading safety concern limits practical applications. To conquer these challenges, amorphous Li3PO4 thin films with thickness of 0–200 nm are directly coated on the surface of Li metal foil via magnetron sputtering. The as-prepared Li3PO4 has almost insulated property with electronic conductivity of 1.4 × 10−10 S/cm and ionic conductivity of 2.8 × 10−8 S/cm. The conformal coating layer Li3PO4 can successfully suppress the lithium dendrites growth and improve its life span. The remarkable improvements of the Li3PO4-coated Li electrodes are mainly attributed to high chemical stability as well as amorphous nature of Li3PO4, which leads layer-by-layer growth Li film rather than islands form dendrites.