Abstract: The properties of BiMo based catalysts with varied composition and structure for the direct selective oxidation of propane to acrolein were investigated. It has been seen by XRD, XPS, in situ FTLRS, and ESR that propane is selectively oxidized to acrolein via propylene intermediate species. The lattice oxygen of the catalysts is the active oxygen species for the selective oxidation of propane to acrolein via propylene; the selectivity and yield of acrolein associate closely with the redox properties of Mo=O species while the activity of Mo=O correlates tightly with its coordinated circumstance. The selective activity of Mo=O is improved in a sequence of locations as distorted octahedral MoO6, corner shared octahedral in koechlinite structure, edge shared octahedral and tetrahedral MoO4 in distorted scheelite structure. The selectivity and yield of acrolein approached 45% and 13.5%, respectively, and the amount of lattice oxygen with selective oxidative activity amounted to 258μmol/g on the optimum catalyst.