Zirconia-supported and bulk-mixed vanadium-antimonium oxide catalysts were used for the oxidation of o-xylene to phthalic anhydride. X-ray diffraction, Raman spectroscopy and photoelectron spectroscopy were used for characterization. It was found that vanadium promotes the transition of tetragonal to monoclinic zirconia. The simultaneous presence of Sb and V on zirconia at low coverage led to a preferential interaction of individual V and Sb oxides with the zirconia surface rather than the formation of a binary Sb-V oxide, while at higher Sb-V contents the formation of SbVO4 took place. Sb-V/ZrO2 catalysts showed high activity for o-xylene conversion and better selectivity to phthalic anhydride as compared to V/ZrO2 catalysts. However, their selectivity to phthalic anhydride was poor in comparison to a V/TiO2 commercial catalyst. The improved selectivity of the Sb-containing catalysts is attributed to the blocking of non-effective surface sites of ZrO2, the decrease of the total amount of acid sites and the formation of surface V-O-Sb-O-V structures.