A Li alloy based artificial coating layer can improve the cyclic performance of Li metal anodes. However, the protective mechanism is not well clarified due to multiple components of the artificial layer and complicated interface in liquid electrolytes. Herein, a single-component Li22Sn5 alloy layer buffered Li anode is paired with a solid-state polymer electrolyte, where a metallic Sn film is sputtered onto the Li anode and the subsequent alloying reaction leads to the formation of a Li22Sn5 phase. During the striping/plating process, the thickness and composition of the Li-Sn alloy passivation layer remain unchanged. Meanwhile, Li+ ions are reduced on the top surface of the Li22Sn5 layer, then the reduced Li atoms immediately pass through the alloy layer, and finally dense Li deposition occurs beneath the protective layer, realizing spatial isolation of the electrochemical reduction of Li+ from Li nucleation/growth. This unique protection mechanism can principally avoid the formation of Li dendrites and efficiently mitigate irreversible reactions between the Li anode and the polymer electrolyte. The synergistic effects lead to a clean and flat surface of the protected Li electrode, enabling a prolonged cycle lifetime over 1300 h at 25 °C at 0.1 mA cm-2 and 0.1 mA h cm-2 in a configuration of symmetrical cells.