Abstract: Carbon dioxide (CO2) is not only one of the primary greenhouse gases but also an abundant carbon resource. The catalytic conversion of CO2 into methanol offers a promising approach to mitigate its adverse environmental impacts and provides a significant pathway for the development and utilization of clean energy.However, the composition and structure of catalysts directly determine the number and distribution of active sites, thereby significantly influencing the efficiency and selectivity of catalytic reactions. To enhance the activity of CuZnAl industrial catalysts in CO2 hydrogenation to methanol, Zr4+ was introduced into the CuZnAl catalyst system via surface impregnation, successfully preparing CuZnAl-xZr catalysts with varying Zr loadings. The role of Zr in regulating the formation of Cu/ZnO interfaces was systematically investigated. The catalyst structure and surface electronic states were characterized using HRTEM, XPS, N2O titration, ICP-OES, and H2-TPR. Results indicate that under reaction conditions of 3 MPa, φ(H2):φ(CO2) = 4, 230 °C, and 40000 mL/(gcat·h), the CZA-2Zr catalyst exhibits the highest methanol production rate of 25.4 mmol/(gcat·h), representing a 23.9% increase compared to the unmodified CZA catalyst. The apparent activation energy of the catalysts remains unchanged, suggesting that the reaction pathway and adsorption energy of intermediates are not significantly altered, and the methanol synthesis activity is determined by the number of active sites on the catalyst surface. As the Zr content increases, the electronic binding energy of the Cu phase on the surface of different CZA-xZr catalysts remains constant, indicating no electronic interaction between Cu and Zr. However, due to the interaction between Zn and Zr, electrons gradually transfer from Zr to Zn. Notably, this electron transfer phenomenon exists even before the catalyst reduction treatment, indicating that Zn and Zr interact during the calcination process. HRTEM results clearly reveal the metal-oxide interfaces in the catalysts and show that the ZnO particle size initially decreases and then increases. The dispersion of Cu0 is negatively correlated with ZnO dispersion, a trend further confirmed by H2-TPR experiments. In conclusion, the CZA-2Zr catalyst exhibits the highest reactant conversion rate due to the highest number of Cu/ZnO interfaces, with ZnO playing a crucial role in the dispersion of Cu0.