The complete benzene oxidation reaction was used to test the reactivity of the Au-V2O5/TiO2 and Au-V2O5/ZrO2 catalytic systems. A strong synergistic effect between gold and vanadia was established when molecular oxygen was used as an oxidizing agent. This effect was more pronounced for titania than for the zirconia support. In the presence of gold, predominantly polyvanadate structures are formed on the surface which are more active in the reaction of complete benzene oxidation in comparison with monovanadate species and bulk V2O5 The deposition of gold leads to a relative lengthening of the V=O bond and to a higher electron delocalization. The B and C parameters calculated from ESR spectra showed no differences for the fresh and spent gold-containing samples, i.e, the catalytic systems seemed to be "stabilized" under the working conditions. The effect of gold on the vanadium oxide reducibility, which could be related to the strength of the V-O-support bond, results in a considerable lowering of the temperature of the V5+ --> V3+ transition. With ozone as the oxidizing agent, an additional lowering of the reaction temperature was achieved and very close values of the catalytic activity on all investigated samples were registered. Upon oxidation by molecular oxygen the oxidant activation takes place on the nanosize gold particles while the vanadium oxide surface species are responsible for the activation of benzene. This is in agreement with synergistic effect between the finely dispersed gold and the surface vanadium structures.