The development of new photoanode materials for hydrogen production and water treatment is in full progress. In this context, hybrid TiO2-Co3O4/Co(OH)2 photoanodes prepared using the sol–gel method using biosurfactants are currently being developed by our group. The combination of TiO2 with a cobalt-based compound significantly enhances the visible absorption and electrochemical performance of thin films, which is mainly due to an increase in the specific surface area and a decrease in the charge transfer resistance on the surface of the thin films. The formation of these composites allows for a 30-fold increase in the current density when compared to cobalt-free materials, with the best TiO2-CoN0.5 sample achieving a current of 1.570 mA.cm−2 and a theoretical H2 production rate of 0.3 µmol.min−1.cm−2 under xenon illumination.