In order to solve the Cu sintering in dimethyl oxalate (DMO) hydrogenation to ethanol, the reaction temperature should be kept at a low value, however, which is unable to show excellent catalytic performance. Herein, the reaction temperature decreased significantly from above 260 to 220°C over Ce‐doping Cu/ZrO2 catalyst, which retained high catalytic efficiency with little influence on the catalyst structure after 96 h on stream. Besides, the structure and performance were changed greatly by adjusting the Cu content. For example, the ethanol selectivity can reach 96.1% based on the 100% conversion of DMO over Ce‐doping Cu/ZrO2 catalysts with 40% content of Cu. Based on systematic characterization, the catalyst possessed higher exposed Cu surface area along with the proper amount of medium acidic sites, avoiding the strong ones that could bring about a series of by‐products. As a result, the formed synergistic effects between Cu sites and medium acidic sites provided the active sites with high efficiency for ethanol synthesis.