Despite numerous efforts involving surface coating, doping, and alloying, maintaining surface stability at high temperatures without compromising intrinsic properties has remained challenging. Here we present a groundbreaking method to address the accelerated oxidation of metals like Cu, Ni, and Fe at temperatures exceeding 200 °C. Inspired by the concept that oxygen (O) itself could effectively obstruct the pathway of O infiltration, the study achieved a significant breakthrough by immobilizing the blocking O. Through extensive calculations considering various elements (C, Al, Si, Ge, Ga, In, and Sn) to anchor O on Cu surfaces, Si emerged as the optimal element. The theoretical findings were validated through systematic sputtering deposition experiments. The introduction of anchoring elements to reinforce Cu–O bonds enabled the formation of an atomically thin barrier on the Cu surface, rendering it impermeable to O even at high temperatures, while preserving its intrinsic conductivity. This remarkable oxidation resistance, facilitated by the impermeable atomic monolayer, opens exciting opportunities for researchers and industries to overcome limitations associated with the use of oxidizable metal films.