An antimony(V) containing alpha-Keggin type acidic polyoxometalate, H4PSbMo11O40, was prepared by reacting NaMoO4, H3PO4 and Sb2O3 in the presence of aqua regia to appraise its reactivity compared to the well known vanadate analog, H4PVMo11O40. Characterization was by X-ray diffraction, MALDI-TOF MS, IR, UV-vis and P-31 NMR spectroscopy. Catalytic redox reactions, such as oxidative dehydrogenation using O-2 and N2O as terminal oxidants were studied and showed very different reactivity of H4PSbMo11O40 versus H4PVMo11O40. It was found by OFT calculations that in contrast to analogous H4PVMo11O40 where vanadium centered catalysis is observed, in H4PSbMo11O40 catalysis is molybdenum and not antimony centered. (C) 2012 Elsevier B.V. All rights reserved.