In the oxidative dehydrogenation (ODH) of propane to propylene VOx-based catalysts prepared by name pyrolysis (FP) showed more selective than those prepared by impregnation. Furthermore, samples prepared by the same method were less active, but more selective when VOx was supported on SiO2 than on Al2O3. In order to assess V local structure, V4+ ions showed useful labels to characterise these catalysts by EPR spectroscopy. Indeed, the spectrum of a (10 wt%V2O5) FP-prepared VOx/SiO2 catalyst was typical of isolated, tetragonally distorted, paramagnetic complexes of V4+ forming a monolayer on the sample surface with a strong out-of-plane V4+-O bond. In a sample with identical composition, but prepared by impregnation, this bond showed a bit weaker. Furthermore, ferromagnetic domains of clustered V ions formed in the latter sample, hindering at least in part the accessibility to the catalytically active V-based centres. This gives evidence of the higher dispersion of V in the sample bulk provided by the FP preparation method with respect to conventional ones. A by far weaker V4+-O bond was revealed by the EPR spectrum of a (10%V2O5) VOx/Al2O3 sample, accounting for its higher oxygen availability, leading to higher activity, but lower selectivity. However, the same catalyst, when prepared by impregnation, showed a ferromagnetic resonance pattern so intense that no EPR spectrum was detectable at all and no information on the V4+-O bond strength was available in that case. Such semi-quantitative index of the V-O bond strength can be used as an index of oxygen availability, as a tool to assess catalytic activity and selectivity to the desired olefin. (C) 2009 Elsevier B.V. All rights reserved.