ZrO2-Cu-based catalysts are active in catalyzing the hydrogenation of CO2 to methanol. Herein, we report Cu facet effects on the catalytic performance of ZrO2/Cu inverse catalysts in CO2 hydrogenation to methanol using various Cu nanocrystals with well-defined Cu morphologies and facets. The ZrO2-Cu interface is the active site, in which the ZrO2-Cu{100} and ZrO2-Cu{110} interfaces exhibit similar apparent activation energies of ∼42.6 kJ/mol, smaller than that of the ZrO2-Cu{111} interface (∼64.5 kJ/mol). Temporal in situ diffuse reflectance infrared Fourier transform spectroscopy characterization results identify the bridge formate hydrogenation as the rate-determining elementary surface reaction under typical reaction temperatures, whose activation energy is similar at the ZrO2-Cu{100} (∼36.3 kJ/mol) and ZrO2-Cu{110} (∼40.5 kJ/mol) interfaces and larger at the ZrO2-Cu{111} interface (∼54.5 kJ/mol). This fundamental understanding suggests Cu facet engineering as a promising strategy to improve the catalytic performance of ZrO2/Cu inverse catalysts for CO2 hydrogenation to methanol.