Vanadia/titania catalysts with varying vanadium content were prepared by impregnation using three different titania carrier materials of varying surface area, The structure of active vanadium species for beta-picoline oxidation was investigated. Vanadium is mainly in the +5 oxidation state as revealed by electron paramagnetic resonance (EPR) and V-51 magic-angle spinning nuclear magnetic resonance (V-51 MAS NMR) spectroscopy techniques. Diffuse reflectance UV-visible (DRUV-vis) spectroscopy and spectral deconvolution enabled identification of at least five different types of vanadium oxide species in these catalysts: monomeric tetrahedral VO43-, polymeric distorted tetrahedral VO3-, square pyramidal V2O5, octahedral V2O62- and V4+ oxide species. While both VO43- and VO3- species are active in beta-picoline oxidation, the latter having a distorted tetrahedral geometry yielded the desired products-picolinaldehyde and nicotinic acid. High surface area, anatase structure for the support and dispersed, distorted tetrahedral vanadium oxide species are the key parameters determining the activity and selectivity of these oxidation catalysts. (C) 2008 Elsevier Inc. All rights reserved.