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The conversion of ethane to ethylene by steam cracking is an energy-intensive process that also produces significant global warming CO2 emissions. An alternative process that is not as energy-intensive and produces significantly less CO2 emissions is the oxidative dehydrogenation of ethane to ethylene by the bulk MoVNbTe mixed oxide catalyst. This paper reviews the current understanding of this catalytic reaction system to determine the nature of the bulk and surface phases of this important catalytic reaction. Although the crystalline M1 phase represents the bulk active phase, much is still unknown about the catalytic active surface sites of the M1 phase under reaction conditions. This review extensively examines the reported studies to date and outlines the experiments still needed to establish a fundamental structure-activity/selectivity relationship for this catalytic system that will guide the development of improved catalysts.