The oxidative dehydrogenation of ethane to ethylene (ODH-Et) is investigated over a high activity-selectivity MoVTeNb mixed oxide. Experiments are performed using a mixture of ethane, oxygen and nitrogen as feedstock, at temperatures from 400 to 480 degrees C, inlet partial pressures of oxygen and ethane from 5.0 to 24.2 kPa, and space-times from 10 to 140 g(cat) h mol(ethane)(-1). Ethylene selectivity varies from 76% to 96%, for an ethane conversion range 17-85%. In a set of experiments at 440 degrees C feeding ethylene instead of ethane, ethylene conversion is from 3% to 14% and COx are the only reaction products, the CO being the dominant species with a selectivity range 73-79%. Kinetic models based on Langmuir-Hinshelwood-Hougen-Watson (LHHW) and Mars-van Krevelen (MvK) formalisms, and combinations of them are developed to describe the ODH-Et. Physicochemical and statistical criteria are employed to contrast the performance of these kinetic approaches. The LHHW kinetics exhibits the best capacity to represent the observations, being a potential model for the conceptual design of ODH-Et reactors in future investigations. Kinetic parameters indicate; (i) ethylene formation is the reaction demanding the lowest activation energy; (ii) total oxidations of ethane are the reactions demanding the largest activation energies; (iii) reaction rates, including that of catalyst oxidation, are weakly affected by changes in the oxygen partial pressure, explaining the high selectivity to ethylene of MoVTeNbO; and (iv) water is the component with the highest affinity to be adsorbed on active sites affecting negatively reaction rates. (C) 2014 Elsevier B.V. All rights reserved.