In thiswork, the lithiophilicity of Li₂O and the capillary action–induced absorption of molten Li are employed to fabricate a hierarchically structured three-dimensional (3D) Li metal electrode comprising Li₂O-coated Cu foam (Li₂O@Cu foam), the unique structural characteristics of which allow one to suppress Li dendrite formation and confine Li movement within the foam matrix. The lithiophilicity of Li₂O@Cu foam is ascribed to the occurrence of in situ interfacial reactions between Li and Cu oxides formed on the surface of Cu foam, and the formation of the Li₂O@Li@Cu hierarchical structure is shown to significantly stabilize the interfacial characteristics of the Li metal anode even in harsh electrochemical environments