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Li metal batteries (LMBs) are known as the ideal energy storage candidates for the future rechargeable batteries due to the high energy density. However, uncontrolled Li dendrites growing during charge/discharge process causes extremely low coulombic efficiency and short lifespan. In this work, a thin lithiophilic layer of Ag was coated on the bare Li surface via a thermal evaporation method, which alleviated volume variations and suppressed Li dendrites growth during cycling. As a result, a long lifespan of 250 h at a current density of 1 mA cm−2 was achieved in the symmetric cell when using the Ag-modified Li foil (Ag@Li). The LiFePO4|Li full cell demonstrated an excellent cycling performance with a high specific capacity of 131 mAh g−1 even after 300 cycles at 0.5 C. This study offers a suitable method for stabilizing Li metal anodes in LMBs.