Copper supported on KIT-6 mesoporous silica was prepared via ammonia evaporation (AE) method and applied for the catalytic hydrogenation of dimethyl oxalate (DMO) to ethylene glycol (EG). The high specific surface area and interconnected mesoporous channels of the support facilitated the dispersion of copper species. The effect of AE temperature and copper loading on the structure of catalysts and induced change in hydrogenation performance were studied in detail. The results showed that both parameters influenced the overall and/or intrinsic activity. The hydrogenation of DMO to EG was proposed to proceed via the synergy between Cu⁰ and Cu⁺ sites and catalysts with high surface Cu⁰/Cu⁺ ratio exhibited high intrinsic activity in the investigated range.