High-quality solid electrolyte interphase (SEI) layers can effectively suppress the growth of Li dendrites and improve the cycling stability of lithium metal batteries. Herein, 1-(6-bromohexanoyl)-3-butylurea is used to construct an organic/inorganic hybrid (designated as LiBr-HBU) SEI layer that features a uniform and compact structure. The LiBr-HBU SEI layer exhibits superior electrolyte wettability and air stability as well as strong attachment to Li foils. The LiBr-HBU SEI layer achieves a Li+ conductivity of 2.75 × 10-4 S cm-1, which is ≈50-fold higher than the value measured for a native SEI layer. A Li//Li symmetric cell containing the LiBr-HBU SEI layer exhibits markedly improved cyclability when compared with the cell containing a native SEI layer, especially at a high current density (e.g., cycling life up to 1333h at 15mA cm-2). The LiBr-HBU SEI layer also improves the performance of lithium-sulfur cells, particularly the rate capability (548 mAh g-1 at 10C) and cycling stability (513 mAh g-1 at 0.5C after 500 cycles). The methodology described can be extended to the commercial processing of Li metal anodes as the artificial SEI layer also protects Li metal against corrosion.