Photoelectrochemical polymerization of poly(3,4-ethylenedioxythiophene), PEDOT, was successfully realized on anodic film grown to 50 V on magnetron sputtered Ti-6 atom % Si alloys. Scanning electron microscopy allowed us to evidence formation of compact and uniform polymer layers on the oxide surface. Photoelectrochemical and impedance measurements showed that photopolymerization allows one to grow PEDOT in its conducting state, while a strong cathodic polarization is necessary to bring the polymer in its p-type semiconducting state. Information on the optical and electrical properties of metal/oxide/polymer/electrolyte junctions proves that PEDOT has promising performance as an electrolyte in metal/insulator/metal structures, while its use in metal/oxide/semiconductor-based devices is negatively influenced by the occurrence of lithium intercalation phenomena during the dedoping process.