Lithium metal is a promising candidate for the high‐energy‐density batteries. However, the high instability of Li against air and dendrite growth during cycling are the key challenges hindering the commercial application of the Li metal battery (LMB). In this study, an organic/inorganic hybrid artificial solid electrolyte interphase (SEI) is introduced on Li surface via dipping Li into 0.1 m zinc trifluoromethanesulfonate solution for 1 min. The key components that endow stability to Li in air for 4 h are analyzed via theoretical calculations. The results confirm that LiF and Zn absorbed with CF3 organic groups can reduce the absorption energy of O2, H2O, and CO2 on Li, thereby limiting the reaction of Li with ambient air. The Li anode with an organic/inorganic hybrid SEI cycles over 600 h at 0.5 mA cm−2 in symmetric cell and 500 cycles in a Li||LiFePO4 full cell, after exposure to ambient air for 4 h. Moreover, the organic/inorganic SEI can facilitate the Li+ transformation and suppress the growth of Li dendrites. The designed air‐stable and dendrite‐free Li metal anodes are promising for practical applications of LMBs.
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