Vanadium pentoxide (V2O5) films were prepared by electrochemical and thermal decomposition of vanadyl sulphate on titanium dioxide covered titanium plates and glassy carbon discs. The prepared material by thermal decomposition showed high surface area and good physical stability; while the electrodeposited films, although being homogeneous, showed poor adhesion. The V2O5 electrodes were chemically and electrochemically stable in aqueous (1M H2SO4 + 1M NaOH, pH 3) and organic (0.1M But4NPF6 + CH3CN) solutions. In both cases, a well defined electrochemical response was observed. At the experimental conditions, the prepared materials were not active for the electrooxidation of toluene. The theoretical modeling suggests that the lack of activity is due to the weak interaction between toluene and the V2O5 surface.