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Iron phosphate catalysts possess a unique selectivity to oxidative dehydrogenation. Unlike ordinary catalysts consisting of molybdenum and/or vanadium, they have no double-bond oxygen species (M&z.dbnd6;O) that are considered to be responsible for the oxygen insertion function and, as a result, for the degradation by C–C bond fission. The defect of iron phosphate catalysts is a lack of oxidation activity. Addition of a very small amount of molybdenum into iron phosphate enhances markedly the oxidation activity without modifying the high selectivity originated from iron phosphate. The marked increase in the activity is ascribable to an increase in the reducibility of iron phosphate, because the reoxidizability of iron phosphate is high enough. It is proposed that the reaction over a Mo-doped iron phosphate is promoted by redox cycle of iron phosphate but not by that of molybdenum phosphate. [Copyright &y& Elsevier]