γ-Alumina-supported copper-manganese oxide was prepared by impregnation and used for carbon monoxide hydrogenation. The Cu-MnOx/γ-Al2O3 catalysts exhibit high catalytic activity in CO hydrogenation, showing markedly enhanced catalytic activities due to the synergistic interaction between the copper and manganese oxide. The results of XRD indicated that the addition of manganese enhances the dispersion of CuO, retards the reduction of CuO and enhances the ability of H2-adsorption, which contribute to the activity of DME synthesis from syngas.