Vanadium oxide supported on zirconia modified with WO3 was prepared by adding Zr(OH)4 powder into a mixed aqueous solution of ammonium metavanadate and ammonium metatungstate followed by drying and calcining at high temperatures. The characterization of prepared catalysts was performed by using FTIR, Raman, and XRD. In the case of calcination temperature at 773 K, for samples containing low loading V2O5 below 18 wt%, vanadium oxide was in a highly dispersed state, while for samples containing high loading V2O5 equal to or above 18 wt%, vanadium oxide was well crystallized due to the high V2O5 loading on the surface of ZrO2. The ZrV2O7 compound was formed through the reaction of V2O5 and ZrO2 at 873 K, and the compound decomposed into V2O5 and ZrO2 at 1,073 K, these results were confirmed by FTIR and XRD. Catalytic tests for 2-propanol dehydration and cumene dealkylation have shown that the addition of WO3 to V2O5/ZrO2 enhanced both catalytic activity and acidity of V2O5-WO3/ZrO2 catalysts. The variations in catalytic activities for both reactions are roughly correlated with the changes of acidity.