Novel photoelectrocatalysts composed of PtRuTiO2/C are prepared by the polymeric precursor method and are characterized by scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy and cyclic voltammetry. The onset potential for methanol oxidation is similar (0.3V vs. RHE) for all of the photoelectrocatalyst layers investigated, although the peak current density is dependent on the layer composition. Irradiation of UV light on the photoelectrocatalyst surfaces enhances the chronoamperometric responses up to 18%, which clearly demonstrates a synergistic effect between the photo- and electrocatalysts. The comparison between all the layers prepared indicates that there is an appropriate ratio of metallic nanoparticles and TiO2 to obtain the best performance of these photoelectroactive layers. These results demonstrate that methanol oxidation is achieved by electro- and photocatalysis using a simple and affordable method. This procedure can be conveniently exploited to enhance the response of direct methanol fuel cell electrodes.