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This paper presents a study of oxidative dehydrogenation of ethane (ODHE) on nanostructured single-component and multicomponent catalysts based on V
5+
, Mo
5+
, and Nb
5+
oxides and produced on alumina by molecular layering. It has been shown that the molybdenum-containing catalysts exhibit higher activity for ODHE in both single-component and binary samples and ensure higher ethylene selectivity. We have demonstrated advantages of ODHE on membrane–catalyst systems in the form of asymmetric ceramic tubes, with catalysts placed inside of them. The membrane–catalyst systems produced by molecular layering offer considerably higher activity and selectivity in ODHE.