The conversion of ethane to ethylene, aromatics, and oxygenates and combustion on supported metal oxide catalysts are discussed. Updated information on the structure and performance of supported oxide catalysts in reactions is offered, underlining the importance of in situ characterization under reaction conditions in order to fully understand the structure and reactivity of supported metal oxide catalysts at molecular level. Support effects, the stability of supported oxide catalysts, molecular structures and oxidation states under reaction conditions, and the effects of metal oxide and additive loading are discussed. The role of terminal and bridging oxygen species is also addressed. Emphasis is placed on the relevance of surface species vs, bulk structure and characterization. A section devoted to new trends in the selective oxidation of ethane to afford high yields and lower working temperatures is included.