The structure and catalytic performance of CuMnZrO2 and Fe-CuMnZrO2 catalysts, which were calcined at different temperature, were investigated by BET, XRD, N2O-titration, XANES, EXAFS and TPR. It was found that the calcination temperature strongly influenced the interaction between the active species and support and hence the structure and catalytic performance. Low calcination temperature yielded poorly crystallized catalysts and favored the formation of a Cu(OH)(2)-like structure. The presence of iron could suppress crystallization of amorphous zirconia and increased the dispersion of copper due to the iron-zirconia interaction within the rise of calcination temperature from 623 to 873 K. However, the addition of iron resulted in the decrease of catalytic activity and selectivity. This could be explained by strong iron-zirconia interaction. It led to the decrease of copper-zirconia interaction, which was responsible for the methanol synthesis, and the decrease of copper-iron interaction, which was responsible for the formation of higher alcohols. (c) 2005 Elsevier B.V. All rights reserved.