Dehydrogenation of propane with steam was investigated using novel LaCoxMn1-xO3 (0 <= x <= 1) perovskite-type oxide (ABO(3)) catalysts. Optimization of the Co substitution ratio (x = 0.2) enabled high propylene yield and selectivity. The perovskite structure of LaCo0.2Mn0.8O3 remained stable during dehydrogenation, as confirmed by XRD measurements. Dehydrogenation of propane over LaCo0.2Mn0.8O3 perovskite catalyst proceeded via reduction-oxidation (redox) of the perovskite oxide; oxidative dehydrogenation of propane consumed lattice oxygen in the perovskite and the consumed lattice oxygen was regenerated by H2O. Surface analyses conducted using XPS and XANES showed that a part of Mn4+ and Co3+ in LaCo0.2Mn0.8O3 was reduced to Mn3+ and Co2+ during the reaction. The LaCo0.2Mn0.8O3 catalyst showed higher selectivity at the same propane conversion compared with the selectivity to propylene over an industrial CrOx/-gamma-Al2O3 catalyst. (c) 2013 Elsevier B.V. All rights reserved.