The combustion of benzene was studied on Pt supported on V2O5-TiO2 samples containing different amounts of V2O5. Vanadium was highly dispersed as V4+ for low V2O5 loadings, forming a vanadia monolayer on titanium dioxide for a V2O5 concentration of about 5% wt. V2O5-TiO2 samples were more active than V2O5 and TiO2 single oxides, and the activity increased with the vanadia content. The platinum dispersion in Pt/V2O5-TiO2 catalysts increased with the V2O5 loading but the activity for the deep oxidation of benzene exhibited an opposite trend. Benzene combustion was a structure sensitivity reaction promoted on larger metallic Pt crystallites which were preferentially formed when the V2O5 content in the sample was decreased.