The environmentally-benign hydrogenation of dimethyl oxalate to produce ethanol has attracted considerable attention recently, and the yield of which remains a challenge for the commonly used Cu-based catalysts. Herein we reported a molybdenum-doped Cu catalyst synthesized by impregnating Mo on the Cu/SiO₂ composite prepared by an ammonia evaporation hydrothermal method, and the Mo₃Cu₂₀/SiO₂ sample exhibited the best compromise between activity and ethanol selectivity, acting as a robust catalyst (460 h time on stream) with a high ethanol yield (∼94 %). It is demonstrated that Mo doping elevates the amount of surface Cu⁺ species through the strong interaction between MoO_x and Cu species, and the balanced Cu⁰/Cu⁺ ratio and enhanced surface acidity resulted by Mo addition afford the high ethanol selectivity through facilitating the dehydroxylation of ethylene glycol, whose activation energy over Mo₃Cu₂₀/SiO₂ is 79.9 kJ/mol, lower than that of Cu₂₀/SiO₂ catalyst (108.1 kJ/mol).