Lithium (Li) metal, as a promising candidate for next‐generation energy storage systems, suffers from an extremely unstable interface that is prone to crack, causing serious corrosion of Li metal and dendrite growth. To address this, a novel dual‐layered interface on the Li metal anode is reported, which is featured with organics (COPO3, (CO)2PO2, and (CO)3PO) on the top and inorganics (Li3PO4) at the bottom. The flexible organic layer with reduced Young's modulus (≈550 MPa) contributes to maintain structural integrity, while the rigid inorganic layer with improved Young's modulus of ≈12 GPa is beneficial to suppress the Li dendrite growth. Accordingly, the protected Li is stabilized to maintain successive electrodeposition over 800 cycles of plating/stripping process at a current density of 2 mA cm−2. Furthermore, the uniform dual‐layered interface tends to prevent the corrosion of air to Li metal, exhibiting almost the same performance as the Li metal treated in the inert atmosphere.