Bulk and TiO2 supported VOPO4 has been investigated for the oxidative dehydrogenation of ethane. XRD, SEM, TG analyses and BET surface area measurements indicated that vanadyl phosphate is highly dispersed on the support up to mono-layer coverage. A fraction of vanadium is present as V(TV) in the calcined samples as evaluated by EPR and TPR techniques. Both reducibility and acidity of vanadium phosphate is strongly enhanced by deposition on TiO2 with respect to the bulk phase, as shown by TPR and NH3 TPD technique, respectively. The supported catalysts are active and selective in the oxidative dehydrogenation of ethane to ethylene in the temperature range 450-550 degrees C, the mono-layer catalyst giving the best performances. Ethylene selectivity decreases with the contact time but increases with the temperature. The former effect indicates that ethylene is further oxidized to CO, at high contact times. The effect of the temperature was attributed to the formation of V(IV), favoured at increasing temperature. This hypothesis was supported by TPR experiments carried out after catalytic tests at 550 degrees C that indicated a significant increase of the fraction of V(IV) after the reaction.