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CO2hydrogenation to methanol is a pivotal route for CO2conversion and fixation, with Cu-based catalysts currently exhibiting superior performance. However, the majority of reported Cu-based catalysts lack a comparison with commercial Cu-based catalysts employed in methanol synthesis from syngas. Furthermore, there are limited research works on the effect of sizes of Cu particle to catalyst performance, especially for inverse Cu catalysts, which is a promising catalyst with highly active ZrOx-Cu interface. By precisely controlling the synthesis method to regulate the particle size of Cu in Zr-Cu inverse catalysts, we illustrated that the copper surface area plays a predominant role in influencing catalytic activity. Additionally, the presence of highly dispersed ZrOxclusters on the surface of Cu particles not only enhances the space-time yield of methanol but also serves to segregate Cu particles and to inhibit sintering. The unique structure of Zr-Cu inverse catalysts leads to comparable reactivity to the commercial Cu catalysts.