A bifunctional V2O5/ZrO2-Al2O3 catalyst of oxidation and dehydration was prepared by wet impregnation method and used in methanol oxidation. The redox, acidity and texture properties of the catalyst were characterized by N-2 sorption, H-2-TPR, NH3-TPD, and XRD. Under mild reaction conditions, V2O5/ZrO2-Al2O3 possesses reasonable acidic and redox properties and exhibits excellent catalytic performance in methanol oxidation with dimethoxymethane, methyl formate and formaldehyde as main products. The catalytic performance of V2O5/ZrO2-Al2O3 is dependent on the catalyst compositions and reaction temperature. V2O5(16.5 wt.%)/ZrO2(8.5 wt.%)-Al2O3 exhibits a good synergistic effect of the redox and acidic properties in the methanol oxidation; over it the selectivity to dimethoxymethane reaches 89.0% with the methanol conversion of 11.1% at 165 degrees C, while the selectivity to methyl formate is 30.0% with the methanol conversion of 66.1% at 215 degrees C. (C) 2010 Elsevier Ltd. All rights reserved.