Abstract: Lithium metal batteries (LMBs) have been widely used in energy storage applications due to their high theoretical energy density. However, the unstable solid electrolyte interphase (SEI) can lead to the formation of lithium dendrites and “dead lithium”, which in turn affects the cycle life and safety of the battery. To address this issue, an artificial SEI is prepared through a polymer coating strategy in this work. The introduction of succinonitrile (SN) can accelerate ion transport by promoting the dissociation of lithium salts. Meanwhile, Li6.5La3Zr1.5Ta0.5O12 (LLZTO) can enhance the mechanical strength of the artificial SEI and promote ion conduction. Furthermore, the competitive coordination between LLZTO and SN can inhibit the corrosion of the lithium anode leading to the formation of an SEI rich in LiF and Li3N. Therefore, the lithium metal anode modified with this artificial SEI can be stably plated/stripped for more than 10,000 hours. The LiFePO4 full cell assembled with the modified anode exerts a discharge specific capacity of 133 mAh g−1 and a capacity retention of 97% after 1,000 cycles at 2 C. Notably, the anode modified with artificial SEI still exhibits excellent electrochemical performance at low-temperature.