Cu/ZrO2 catalysts with amorphous, monoclinic and tetragonal zirconia as supports were prepared and characterized by XRD, H-2-TPR, N2O-titration. FF-IR and CO hydrogenation techniques. It was found that zirconia polymorphs had a great influence on the interaction Of Cu and ZrO2. Though it had the lowest surface area, tetragonal zirconia supported copper catalyst showed the highest copper dispersion and the best catalytic performance for methanol synthesis from CO hydrogenation. The formate and methoxyl species were evidenced as intermediates by FT-IR in the case of CO hydrogenation, and the formate-to-methoxyl mechanism was suggested for methanol synthesis on Cu/ZrO2 catalyst. (c) 2004 Elsevier B.V. All rights reserved.