Titanium oxide (Ti(O)) xerogel films functionalized by protoporphyrin IX (PPIX) and ferrocene carboxylic acid (FCA) were deposited on indium tin oxide (ITO) electrodes following a sol–gel synthesis. PPIX and FCA were first complexed to titanium oxide precursors, which were then subjected to hydrolysis to obtain a homogenous Ti(O) polymeric network gel doped with PPIX and FCA. The Ti(O) film cast on the ITO electrode has been characterized by UV–Vis absorption, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy and cyclic voltammetry. Illumination of the PPIX doped Ti(O) films on the ITO electrode immersed in aqueous electrolytes onsets photoinduced electron transfer reactions, and a cathodic photocurrent was observed in most cases. This photocurrent response was investigated in detail using a kinetic model. Preliminary investigations of oxygen reduction, lithium and proton insertion into the Ti(O) film have also been carried out.