Pure and K-doped vanadia/titania prepared by different methods have been studied in order to elucidate the role of vanadia species (monomeric, polymeric, bulk) in catalytic toluene partial oxidation. The ratio of different vanadia species was controlled by treating the catalysts in diluted HNO3, which removes bulk vanadia and polymeric vanadia species, but not the monomeric ones, as was shown by FT-Raman spectroscopy and TPR in H2. Monolayer vanadia species (monomeric and polymeric) are responsible for the catalytic activity and selectivity to benzaldehyde and benzoic acid independently on the catalyst preparation method. Bulk V2O5 and TiO2 are considerably less active. Therefore, an increase of the vanadium concentration in the samples above the monolayer coverage results in a decrease of the specific rate in toluene oxidation due to the partial blockage of active monolayer species by bulk crystalline V2O5. Potassium diminishes the catalyst acidity resulting in a decrease of the total rate of toluene oxidation and suppression of deactivation. Deactivation due to coking is probably related to the Brønsted acid sites associated with the bridging oxygen in the polymeric species and bulk V2O5. Doping by K diminishes the amount of active monolayer vanadia leading to the formation of non-active K-doped monomeric vanadia species and KVO3.