A series of CuO catalysts supported on CeO2 with different morphologies (nanorod, nanocube and hydrangea-like) were tested for the CO2 hydrogenation into methanol. Remarkable morphology-dependent CuO-CeO2 interaction was observed, which was associated with the types and concentrations of copper species. The best performance was obtained over the CuO/hydrangea-like-CeO2 catalyst, giving CO2 conversion of 15.6 % and methanol selectivity of 92.4 % at 260 °C and 3 MPa. The enhanced activity was due to the largest amount of small particle size of copper species, which was responsible for the facile activation of H2. Additionally, the Cu2+-Ov-Cex species facilitated the generation of oxygen vacancies and hydroxyl groups, these two species favored formate production and further hydrogenation to methanol. Moreover, in situ diffuse reflectance infrared fourier transform spectroscopy (in situ DRIFTS) results revealed that the both monodentate formate (m-HCOO*) and bidentate formate (bi-HCOO*) were key and necessary intermediate of CO2 hydrogenation to methanol. The proposed predominate reaction pathway was m-HCOO*→ b-*OCH3 → CH3OH and the minor one was bi-HCOO* → t-*OCH3 → CH3OH.