Vanadium containing catalysts were prepared on silica at vanadia loadings from 1.25 to 12.5% and using different vanadia precursors. Even though no V2O5 crystallites were detected via X-ray powder diffraction or Temperature programmed reduction on the catalysts at vanadia loadings up to 5%, an increased propylene formation rate per gram of vanadium was recorded for catalysts as their surface area increased with decreasing vanadia loading. The propylene formation rate per gram vanadium for all catalysts could be correlated with the total surface area of the catalysts, irrespective of the vanadia loading or vanadia precursor used in the preparation. V-Nb/MCM-41 was found to be the catalyst with the highest propylene formation rate per gram of vanadium. In addition it is also a highly selective catalyst for propane oxidative dehydrogenation resulting in a propylene selectivity of 57% at 30% propane conversion.