Abstract Li has garnered enormous attention for next‐generation Li metal batteries owing to its remarkable theoretical capacity. Unfortunately, as an anode, Li suffers from serious safety issues and fast capacity fading due to the formation of Li dendrites, which hinders the practical application of Li anode. Herein, a LiAlO2‐PVDF composite modification layer is fabricated on the surface of Li metal to enhance its stability and electrochemical performance. Benefitting from the synergetic effects of high Li+ conductivity, high Li+ transference number, excellent mechanical properties, superior chemical durability, and compactness of the modification layer, the LiAlO2‐PVDF@Li electrode delivers an ultra‐long lifespan and a high capacity retention rate in the LiAlO2‐PVDF@Li│LiFePO4 full cell. The proposed strategy provides a new alternative anode for Li metal batteries with high performance and scalable production.
