Despite the ever-growing demand for Li metals as next-generation Li battery electrodes, little attention has been paid to their oxidation stability, which must be achieved for practical applications. Here, a new class of printable solid electrolyte interphase mimic (pSEI) for antioxidative Li metal electrodes is presented. The pSEI (approximate to 1 mu m) is directly fabricated on a thin Li metal electrode (25 mu m) by processing solvent-free, UV polymerization-assisted printing, exhibiting its manufacturing simplicity and scalability. The pSEI is rationally designed to mimic a typical SEI comprising organic and inorganic components, in which ethoxylated trimethylolpropane triacrylate and diallyldimethylammonium bis(trifluoromethanesulfonyl)imide are introduced as an organic mimic (acting as a moisture-repellent structural framework) and inorganic mimic (allowing facile Li-ion transport/high Li+ transference number), respectively. Driven by the chemical/architectural uniqueness, the pSEI enables the thin Li metal electrode to show exceptional antioxidation stability and reliable full cell performance after exposure to humid environments.