Vanadium oxide-zirconia catalysts were prepared by dry impregnation of powdered Zr(OH)(4) with an aqueous solution of NH4VO3. The surface characterization of prepared catalysts was performed using FTIR, DSC, V-51 solid state NMR, and XRD, and by the measurement of surface area. The addition of vanadium oxide up to 9 mol% to zirconia shifted the phase transitions of ZrO2 from amorphous to tetragonal toward higher temperatures due to the interaction between vanadium oxide and zirconia. On the basis of results of IR, XRD, and DSC, it is concluded that the content of V2O5 monolayer covering most of the available zirconia is 9 mol%, giving 2.3 V2O5 molecules/nm(2). Since the ZyO(2) dispersed vanadium oxide, the crystalline V2O5 was observed only with the samples containing V2O5 content exceeding the formation of complete monolayer (9 mol%) on the surface of ZrO2. For the samples calcined at 673 K the acidity and surface area increase abruptly upon the addition of 0.2 mol% V2O5 to ZrO2, and then both of them increase with increasing V2O5 content up to 5 mol%, showing the presence of Bronsted and Lewis acid sites on the V2O5/ZrO2 catalyst.