Abstract Small gold nanoparticles supported on ZnO have been identified as highly active and selective catalysts for the green synthesis of methanol from CO2 and H2. Furthermore, they can serve also a model system for the mechanistic understanding of methanol synthesis on the industrial Cu/ZnO catalyst. The dynamic changes in the structure of Au/ZnO upon exposure to methanol synthesis gas mixtures were studied using a combination of TAP reactor and near edge X-ray absorption spectroscopy (XANES) measurements at the Zn LIII edge, both in CO2/H2 and CO/H2 gas mixtures. TAP measurements indicated that CO can create significant amounts of O-vacancy defects in ZnO at 240°C, while CO2 can re-oxidize a pre-reduced catalyst or maintain this state in the presence of strongly reducing gases (CO and H2). Furthermore, CO2 present as reactant or resulting from the reactive removal of surface lattice oxygen by interaction with CO can be deposited on the pre-reduced Au/ZnO surface as stable adsorbed carbon containing species, e.g., as surface carbonates, which decompose at T≥250°C. In situ XANES measurements at the Zn LIII edge revealed that ZnO is significantly reduced during reaction, both in CO2/H2 and CO/H2 gas mixtures, but with the extent of the reduction being more pronounced in CO/H2 than in CO2/H2. These results will be critically discussed in the light of previous findings on the role of ZnO reduction in the activity of methanol synthesis catalysts.