context: In summary, we developed a formation method of a Li protective artificial SEI layer to form a LiF and polymeric composite protection layer directly on lithium metal foil using the electrochemical reaction between the Li and the sacrificial PTFE film by using roll-pressing. The roll-press process is facile, cost-effective, eco-friendly and a mass and large-area scalable process. The composite protection layer composed of a LiF-rich layer and polyene/unsaturated fluoropolymer rich layer could significantly improve the electrochemical properties of LMBs. The LiF@Po protection layer provides a stable interface between the Li metal and the electrolyte, enabling improved Li plating/stripping behavior and ultra-long cycling stability in both the Li‖Li symmetric cell and Li‖LCO/Li‖NCM full cells. In particular, the full cell with the NCM-811 cathode and LiF@Po–Li anode exhibits reasonable electrochemical performance even with transition metal dissolution. The material design strategies presented here could provide important avenues for forming an artificial SEI layer in various applications not only in Li metal systems but also in other metal systems including sodium and potassium.