The process of methanol synthesis based on the hydrogenation of CO2 was investigated over binary Cu/ZnO catalyst materials, prepared by applying a novel electroless plating fabrication method. The activity of the produced catalytic samples was determined at temperature range between 200 and 300 degrees C and the feedstock conversion data were supplemented with a detailed microstructure analysis using high-resolution transmission electron microscopy(HRTEM), X-ray powder diffraction(XRD) and Cu and Zn K-edge, X-ray absorption near-edge structure (XANES) measurements and extended X-ray absorption fine-structure (EXAFS) measurements. It was confirmed that the disorder in the Cu crystallites created unique geometrical situations, which acted as the additional reactive centres for the adsorption of the reactant molecule species. Copper and zinc structural synergy (spill-over) was also demonstrated as being crucial for the carbon dioxide's activation. EXAFS and XANES results provide strong evidence for surface alloying between copper and zinc and thus the present results demonstrate new approach applicable for explaining metal-support interactions. [GRAPHICS] .