The formation of PdZn bimetallic alloys on ZnO, TiO₂ and Al₂O₃ supports was investigated, together with the effect of alloy formation on the CO₂ hydrogenation reaction. The chemical vapour impregnation (CVI) method produced PdZn nanoparticles with diameters of 3–6 nm. X-ray photoelectron spectroscopy and X-ray diffraction revealed the changes in the structure of the PdZn alloy that help stabilise formate intermediates during methanol synthesis. PdZn supported on TiO₂ exhibits high methanol productivity of 1730 mmol kg_cat⁻¹ h⁻¹ that is associated with the high dispersion of the supported PdZn alloy.