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Dehydrogenation of ethane over perovskite oxide catalysts was investigated using the redox of perovskites and H₂O as an oxidizing agent. The La_0.8Ba_0.2MnO_3−δ (LBMO) perovskite showed a high catalytic activity for dehydrogenation of ethane. Periodic dry (without H₂O)–wet (with H₂O) operation tests revealed that dehydrogenation of ethane in the presence of H₂O over LBMO proceeded via the Mars–van Krevelen (MvK) mechanism. Under the wet condition with D₂O instead of H₂O, D₂ formation was verified, demonstrating that reactive lattice oxygens in LBMO contributed to the dehydrogenation reaction and that they were regenerated by water. Isotopic transient tests with H₂¹⁸O and in situ X-ray absorption fine structure measurements revealed that the reduction and oxidation of Mn in LaMnO₃ and LBMO occurred under the reaction atmosphere and that the partial replacement of the La sites with Ba …