Infrared spectroscopy was used to obtain information on the mechanism of the selective oxidation of toluene and o-xylene over vanadium oxide catalysts. The interaction of these aromatic hydrocarbons and the products benzaldehyde and o-tolualdehyde with the surface of a V2O5/TiO2 monolayer catalyst was investigated at different temperatures under conditions comparable to those of the catalytic reaction. The infrared results obtained for each of these compounds showed a great resemblance, indicating that their oxidation proceeds along the same reaction path. Coordinatively adsorbed aldehydes, carboxylate-like structures, and benzoate species could be identified as intermediates on the surface of the catalysts. On the basis of the spectroscopic observations a possible reaction mechanism has been proposed.