In order to investigate the catalytic properties, V238Nb10.7O32.7, VNb9O25 and solid solutions of V2O5 in TT-Nb2O5 were prepared by thermal decomposition of freeze-dried oxalate precursors. The samples were characterised by X-ray diffraction and surface area determination. The crystalline samples are capable of the intercalation of sodium and lithium ions from solution. Above a temperature of about 500 degrees C, in dependence on the oxygen partial pressure a reversible release and uptake of oxygen without a structural variation takes place. The catalytic properties have been evaluated for the oxidative dehydrogenation (ODH) of propane and propene. There are only small differences in the catalytic activity of the different crystalline samples. Because of the relative high starting temperature, a selective catalytic oxidation of propane to propene is hardly observed. (C) 2011 Elsevier Ltd. All rights reserved.