Novel vanadium oxide based catalyst derived from he open-framework solid, [Co3V18O42(H2O)(12)(XO4)] center dot 24 H2O (X = V, S) (1) catalyses oxidative dehydrogenation of propane to propylene. Catalyst activity was evaluated in the temperature range 250-400 degrees C with varying gas hourly space velocity (GHSV). At 350 degrees C and GHSV of 9786 h(-1) and at 1.3% propane conversion the selectivity to propylene was 36.8%. The major products obtained were propylene and COx(CO2 and CO). The ratio of the propylene to COx depended directly on the catalytic sites present. Thus, as the amount of the catalyst was decreased, the conversion decreased with an increase in the propylene selectivity and a decrease in the selectivity to carbon oxides-COx. The catalyst has been characterized by temperature programmed reduction and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS).