Abstract: The accelerated advancement of industrial civilization has significantly exacerbated energy consumption and environmental pollution. Excessive CO₂ emissions have precipitated substantial global economic losses. Consequently, strategies for mitigating CO₂ emissions and enhancing CO₂ utilization efficiency have attracted widespread international attention. Among these strategies, the catalytic hydrogenation of CO₂ to methanol has emerged as a particularly promising approach due to its potential for establishing a closed carbon cycle. Copper-based catalysts, featuring metallic Cu as the active sites dispersed on metal oxide supports, have demonstrated considerable industrial relevance in this domain.Recent investigations have revealed that metal oxide supports are not merely inert substrates but actively participate in catalytic reaction mechanisms. To systematically evaluate the influence of diverse metal oxide supports on CO₂ hydrogenation to methanol, a series of mesoporous Cu-supported catalysts were synthesized employing an ordered macroporous templating method. SEM and TEM analyses confirmed that each catalyst possessed a well-defined three-dimensional ordered macroporous structure, characterized by pore diameters of approximately 220 nm. XRD patterns indicated the reduction of CuO to metallic Cu, which exhibited remarkable stability over 100 hours of reaction, showing only a marginal increase in particle size. This observation suggests robust structural integrity. XPS analyses revealed that the dispersed metal oxide nanoparticles on the Cu surface exhibited distinct structural characteristics compared to their bulk counterparts. CO₂-TPD and NH₃-TPD analyses demonstrated that the ZrO₂-9Cu catalyst possessed strong basic sites, which inhibited the adsorption of reactive intermediates, resulting in the lowest methanol selectivity （63.8%）. Conversely, the Cr₂O₃-9Cu catalyst exhibited an abundance of strong acidic sites, suppressing methanol formation and consequently yielding the lowest methanol production rate （66.58 g_MeOH/（kg_cat·h））. Notably, the Al₂O₃-9Cu catalyst achieved the highest methanol yield of 270.64 g_MeOH/（kg_cat·h）. This performance indicates that an optimally balanced distribution of acidic-basic sites, coupled with moderate reaction temperatures, is conducive to enhanced methanol synthesis.FT−IR spectroscopy was employed to elucidate the mechanistic pathways of CO₂ hydrogenation to methanol. Spectroscopic evidence confirmed that the ZrO₂-9Cu, ZnO-9Cu, Al₂O₃-9Cu, and Cr₂O₃-9Cu catalysts follow the formate reaction pathway. In contrast, the CeO₂-9Cu catalyst exhibited a prominent carboxylate （COO—） infrared absorption peak at 1322 cm⁻¹, indicative of a reaction pathway involving the reverse water-gas shift （RWGS） reaction followed by CO hydrogenation, commonly termed the RWGS + CO-Hydro pathway.