A comparative study of the catalytic oxidative dehydrogenation of propane by a novel polyoxovanadate based open-framework material (Co-POV)-[Co3V18O42 (H2O)(12)(XO4)]center dot 24H(2)O (X = V, S), which is composed of nanometer size vanadium oxide clusters interlinked by cobalt oxide {-O-Co-O-} motifs, showed that Co-POV has superior catalytic property as compared to its individual metal oxide constituents, vanadium oxide and cobalt oxide, and their mixture, with high propylene selectivity.