The ability of using niobium oxide (Nb2O5) as a support for preparing surface metal oxide species and testing the catalyst for the ODH of propane was done in the present study. Chromium oxide was used as the representative surface metal oxide species. To test the objective several loadings of Cr2O3/Nb2O5 were prepared by the incipient wetness impregnation technique. Surface area analysis, Raman, X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) spectroscopy and TPR studies were used to characterize the sample. It was. observed that surface chromium oxide species are formed similar to those on other oxide supports and similar monolayer coverages were achieved. However, the reduction characteristic (T-max temperature) was different due to the change in the Cr-O-support bond. The ODH of propane over the Cr2O3/Nb2O5 catalysts revealed that the activity increased up to monolayer coverage and then decreased due to the presence of Cr2O3 crystals. Similar observations were seen for the V2O5/Nb2O5 and MoO3/Nb2O5 catalysts. The turnover frequency (TOF) was independent of coverage for the surface chromium, vanadium and molybdenum oxide species on Nb2O5. The constant TOF suggests the structure insensitivity of this type of reaction. The propene selectivities were high and relatively constant for the Cr2O3/Nb2O5 catalysts revealing the higher yields that can be obtained on this series of catalysts compared to the Cr2O3/Al2O3 and Cr2O3/TiO2 catalysts. Additional studies involving tungsten and molybdenum oxide additives on 1% Cr2O3/Nb2O5 reveal the effect of exposed support surface on the propene selectivities.