Various catalysts containing niobium and vanadium oxides supported on alumina were prepared by wet impregnation via aqueous solution using several precursors. The total loading of V and Nb oxides were below their dispersion limit on alumina. Vanadyl sulfate, ammonium metavanadate and ammonium niobate(V) oxalate were the precursors for supported vanadia and niobia. The reduction/oxidation properties were studied by conventional TPR/TPO and TPR/TPO-Raman. Surface vanadium oxide species tend to increase their polymerization degree upon TPR/TPO cycles. A broad weak feature near 900 cm(-1) appears associated to V3+-O-Al3+ bond vibration in the reduced vanadia-alumina catalysts. Niobia appears to retard vanadia reduction. Regarding supported niobia, a fraction of surface niobia is significantly more reducible than surface vanadia and another fraction is significantly less reducible. The more reducible nobia appears associated to an incipient Nb-Al-O phase that may account for a fluorescence background observed in the Raman spectra. The less reducible mobia phases appears associated to dispersed niobium oxide species on alumina. Niobium has an effect on vanadia reduction profiles in VNb/Al2O3 System. (c) 2006 Elsevier B.V. All rights reserved.