CuO/ZnO/Al2O3 catalysts with mesoporous Al2O3 as support were prepared by precipitation-deposition method using cupric nitrate and zinc nitrate as raw materials. Catalysts possessing different active component morphologies (globular clusters and rod-like structure) were obtained by changing calcination time and used for CO/CO2 hydrogenation reaction. The catalysts were characterized and tested by XRD, BET, N2 adsorption-desorption, TEM, H2-TPR, CO2-TPD, NH3-TPD and FTIR. The results showed that the morphology of the active components affects the CuO grain size, specific surface area, pore size and reduction performance of the catalyst and has a great influence on the relative quantity of acid sites and basic sites of the catalysts. The catalyst with globular clusters has high dispersion of active components, easy to reduce, more basic sites and less acid sites, which is favorable for the formation of methanol. While the rod-like catalyst has uneven pores, less basic sites and more acid sites, which is more conducive to the formation of dimethyl ether (DME). The activity test results revealed that the catalyst with globular clusters exhibited high methanol selectivity (95.05%) and low DME selectivity (4.18%). The rod-like catalyst displayed the opposite trend with high DME selectivity (75.41%) and low methanol selectivity (12.81%).