A kinetic study of the oxidative dehydrogenation of butane over V/MgO catalysts has been carried out. The rate equations for the oxidation of each of the hydrocarbons in the proposed reaction network were obtained independently, and specific experiments were also performed to evaluate inhibition effects of the reaction products on the butane reaction rate. Several competing kinetic models were statistically analyzed. The best fit was obtained with a dual-site Mars-van Krevelen model, the suitability of which was also tested in separate anaerobic experiments. Furthermore, this model was able to predict reactor performance under conditions far removed from those employed in the differential reactor experiments used to obtain the kinetics.