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The use of hydrogen as an energy vector and raw material for “very clean liquid fuels” manufacturing has been assessed by the catalytic conversion of CO2 to methanol over copper based catalysts. A systematic evaluation of copper based catalysts, prepared varying the chemical composition, has been carried out at 0.1–5.0 MPa of total pressure and in the range of 453–513 K by using a semi-automated LAB-microplant, under CO2/H2 reactant mixture (1/3), fed at GHSV of 8.8 NL∙kgcat−1∙h−1. Material’s properties have been investigated by the means of chemical-physical studies. The findings disclose that the addition of structure promoters (i.e., ZrO2/CeO2) strongly improves the textural properties of catalysts, in term of total surface area and exposure of metal surface area (MSA), also reducing the sintering phenomena. The results of the catalytic study clearly prove a structure-activity relationship at low reaction pressure (0.1 MPa), while at higher pressure (3.0–5.0 MPa) the reaction path is insensitive to structure and chemical composition.