Abstract The active site of a solid catalyst varies sensitively with the catalyzed reaction. Herein, using experimentally measured elementary surface reaction kinetics of CO2 or CO hydrogenation reactions over a ZnO-ZrO2 catalyst under working conditions in combinations with comprehensive structural characterizations and theoretical simulations, we unveil the distinctly different active sites in catalyzing the CO2 or CO hydrogenation to methanol reaction. Zn2+ cations with different local environments are present on the ZnO-ZrO2 surface, including Zn1 single atoms exclusively with a Zn-O-Zr local structure and Znn clusters with both Zn-O-Zr and Zn-O-Zn local structures. The -Zr-O-Zr- structure bonded to the Znn clusters is more easily to be reduced than that bonded to the Zn1 single atoms. The Zn1-single atom (-Zr-O-Zn-O-Zr-) is the active site for catalyzing the CO2 hydrogenation to methanol reaction, whereas the Znn cluster bonded to an in situ formed -Zr-Vo-Zr- structure (-Zn-O-Zn(-O-Zr-Vo-Zr-)-O-Zr-) is the active site for catalyzing the CO hydrogenation to methanol reaction. These results provide a reliable and effective methodology of elementary surface reaction kinetics for identifications of active sites of working catalysts in complex reactions and unveil how sensitively the active site structure varies with the catalyzed reaction.