A dendritic PdCu/CeZrO (PdCu/CZ-3) catalyst with uniform spherical morphology was prepared for boosting the catalytic performance of CO hydrogenation to methanol (MeOH). The open dendritic pore channels and small particle sizes could reduce not only the diffuse resistance of reactants and products but also increase the accessibility between the active sites (PdCu and oxygen vacancy) and the reactants (H and CO). More spillover hydrogen could be generated due to the highly dispersed PdCu active metals over the PdCu/CZ-3 catalyst. PdCu/CZ-3 can stimulate the generation of more Ce cations, which is beneficial to produce more oxygen vacancies on the surface of the CZ-3 composite. Spillover hydrogen and oxygen vacancy could promote the formate and methoxy routes over PdCu/CZ-3, the primary intermediates producing MeOH. PdCu/CZ-3 displayed the highest CO conversions (25.5 %), highest MeOH yield (6.4 %), highest PdCu-TOF (7.7 h) and superior 100 h long-term stability than those of other PdCu/CeZrO analogs and the reference PdCu/CeO and PdCu/ZrO catalysts. Density functional theory (DFT) calculations and in situ DRIFTS were performed to investigate the CO - MeOH hydrogenation mechanism.