A highly efficient ordered mesoporous CuZn/hierarchical porous silica (HPS) catalyst was prepared by an impregnation-ammonia evaporation method. The presence of Zn species prompted the dispersion of copper species and the formation of more Cu+ species in reduced catalyst. Moreover, the larger mesopores in HPS significantly enhanced the accessibility of active sites for the dimethyl adipate adsorption. The cooperative effect of zinc species and the HPS structure contributed to the superior catalytic performances of CuZn/HPS in dimethyl adipate hydrogenation.