In order to investigate the methanol synthesis reaction from CO 2 /H 2 , a comparative study of the reactivity of formate species on different types of catalysts and catalyst supports has been carried out. Formic acid was adsorbed on water–gas shift catalysts, Cu/ZnO/Al 2 O 3 methanol synthesis catalyst and ZnO/Al 2 O 3 support, Cu/ZnO/ZrO 2 and Cu/ZnO/CeO 2 methanol synthesis catalysts as well as their corresponding supports ZnO/ZrO 2 and ZnO/CeO 2 . Superior reactivity and selectivity of dedicated methanol synthesis catalysts was evidenced by their behavior during the subsequent heating ramp, when these samples showed the simultaneous presence of formates and methoxy species and a higher stability of these reaction intermediates in the usual temperature range for the methanol synthesis reaction.