HZSM-5 supported copper-molybdenum oxide prepared by an impregnation method has been applied for the first time in the hydrogenation of CO2. The effect of the loading of Mo, the reaction temperature and the stability of hydrogenation of CO2 were investigated. The results indicate that adding a small amount of Mo (Mo/Cu = 1/2 wt) markedly enhances the catalytic activity. The highest DME selectivity was more than 70%. The change of species on the catalyst surface due to the addition of Mo was also investigated by in situ DRIFT.