We report on the low-temperature synthesis of submicron-sized Cu3N powder produced from CuO and NaNH2 powder mixture by heating at 150–190 °C in a Teflon-sealed autoclave. The structure was the anti-RuO3 type with a lattice parameter of 0.3814(1) nm, and strong optical absorption was observed below ∼1.9 eV. This synthesis method has the potential of facile control of the reaction with less use of ammonia sources.