Oxidative dehydrogenation of ethane (ODHE) to ethylene was investigated over a series of alumina supported molybdophosphoric acid (MPA) catalysts. The MPA was transformed into surface Mo oxides on Al2O3 when subjected to calcination at 600°C. The catalysts were characterized by N2-adsorption, XRD, FT-IR spectroscopy and TPR techniques. The results showed that MPA loading and the source of Mo precursor had a clear influence on the catalytic performance. The evaluation of the catalysts for ODHE at temperatures between 450 and 550°C revealed superior ethane conversion (X∼24%) and ethylene selectivity (S = ca. 65%) over 20 wt % MPA/Al2O3 catalyst. The transformation of MPA into finely dispersed Mo oxides on Al2O3 appeared to be responsible for this improved performance.