Catalysts with the CeTi bimetallic modified dendritic mesoporous silica nanospheres (CTD) as supports, and the PdZn as active metal phase, PdZn/CTD catalysts with higher Pd metal dispersion and more oxygen vacancies were synthesized for efficient CO2 hydrogenation to methanol (MeOH). The modification of PdZn/CTD using CeTi metals can increase the dispersion of PdZn and improve the Ce3+/Ce4+ ratios. Higher active metal dispersion of PdZn/CTD catalyst is conducive to more H2 adsorption and to the expose of activation sites. Higher Ce3+/Ce4+ ratio of PdZn/CTD is beneficial to generate more oxygen vacancies, which can adsorb and activate CO2 molecules efficiently. The optimized PdZn/CTD catalysts exhibit superior CO2 conversion (33.6 %), MeOH selectivity (32.9 %), MeOH yield (11.1 %), TOF value (22.5 h−1), space–time yield (STY) (4.44 molMeOH kg-1 h−1) and 100 h long-term stability. Besides, through in-situ DRIFTS, HCOO* and CH3O* species are found to be the primary intermediates of the CO2 hydrogenation to MeOH reaction over the PdZn/CTD catalysts.