The use of TiO2 photoanodes sensitized with ruthenium(II) polypyridine complexes bearing phosphonic acid anchoring groups has been investigated in the context of photoinduced hydrogen generation. The photoanodes sustained 240 h of irradiation without undergoing appreciable hydrolysis and decomposition in an aqueous environment at pH 3. While the use of organic sacrificial donors, like ascorbic acid, considerably enhanced the photoanodic response, the exploitation of iodide was more problematic because the adsorption of photogenerated I-3(-) from aqueous media favored charge recombination with conduction band electrons, thus limiting the efficiency of the photoelectrosynthetic device. However, experiments performed in a three-compartment cell, where the photolectrode was in contact with an organic solvent, showed a remarkable photocurrent, with an electrolysis yield close to 87%.