The catalytic performances of vanadia catalysts with 15wt percent V supported on TiO2 and (15wt percent V+5wt percent Mo) supported on TiO2 in oxidative dehydrogenation (ODH) of n-butane were investigated. The catalysts were characterized by means of TPD-NH3, TPR-H2, UV-Vis and BET. Testing of samples showed that MoV catalyst was much more active than the V based catalyst for the reaction. The presence of Mo allowed a better dispersion of active species on the support surface, increased isolated monomeric VOx units with tetrahedral coordination and also increased amount of Me-O-Ti bonds. These factors could be responsible for the higher reactivity of MoV catalysts to the reaction.