Understanding the nature of copper active sites and structural evolution in preparation is crucial to rational design of copper catalysts for ethylene carbonate hydrogenation. The Cu/MCM-41 catalysts were prepared to focus on the evolution of Cu species by varying the Cu/Si mass ratio in the deposition-precipitation process. The synthesis mechanism, physicochemical properties as well as quantitative Cu active species over Cu/MCM-41 catalysts were systematically characterized and the catalytic performance was evaluated to get insight into structure-activity relationship for the ethylene carbonate (EC) hydrogenation. The results indicated that the Cu/Si ratio significantly influenced the formation of Cu-0 and Cu+ active sites over the catalysts, which are derived from the CuO and Cu silicates, respectively. The appropriate textural structures, high surface Cu dispersion and synergetic effect between Cu-0 and Cu+ sites of the 0.7Cu/MCM-41 catalyst resulted in an outstanding performance for EC hydrogenation, with turnover number (TON) of 18.63 and 13.82 to ethylene glycol and methanol.