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Ethylene glycol (EG) synthesis from dimethyl oxalate (DMO) hydrogenation is a sustainable method compared with the production by petrochemical technology. The Cu/ZnO/SiO2 catalysts prepared by deposition precipitation method have been characterized by XRD, SEM, H2-TPR, and N2 physisorption. Under optimum reaction conditions, a DMO conversion of 100% and EG selectivity of 98% was obtained on the CuZn-5 catalyst. The present work also demonstrates a feasibility method to produce ethanol from DMO hydrogenation. On the catalyst of CuZn-15, the conversion of DMO can reach to 99% with the ethanol selectivity of 64% under the optimized reaction conditions.