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To minimize greenhouse gas emissions, efficient carbon dioxide capture and utilization need to be addressed. In this study, to determine the structure–activity interplay, three different promising catalytic systems for the CO2hydrogenation process were synthesized using mesoporous silica SBA-15 as a support material: copper-based catalyst with zinc, indium-based catalyst with palladium and iron-based catalyst with potassium. The role of metal–metal oxide interaction has been showed. The use of Cu/Zn catalytic system and SBA-15 allowed to obtain very small crystallite size of tenorite and zinc oxide, good dispersion of active phases with strong basic sites. In order to find the most effective catalyst providing the maximal methanol yield and selectivity, these catalytic systems were compared under the same reaction conditions (250 °C, 20 bar, H2to CO2molar ratio 4 to 1) using fixed-bed tubular micro-activity reactor. Results showed that the highest methanol yield can be obtained with Cu/Zn/SBA-15 catalyst as might be expected according to obtained characterization.