CuO-ZnO-ZrO2/HZSM-5 bifunctional catalysts were prepared by a facile route of solid-state reaction and tested for one-step synthesis of dimethyl ether (DME) from CO2 hydrogenation. The effects of calcination temperature (300–600°C) on the physicochemical and catalytic properties of the bifunctional catalysts were investigated by XRD, N2 adsorption, XPS, N2O chemisorption, SEM, H2-TPR, NH3-TPD, and CO2-TPD techniques. The results show that both the CO2 conversion and DME selectivity of the bifunctional catalysts decrease with the increase in calcination temperature, which can mainly be attributed to the decrease of metallic copper surface area (SCu), adsorption capacity of CO2, specific surface area, and reducibility of CuO.