Visible light-responsive TiO2 (Vis-TiO2) thin films were prepared by a radio frequency magnetron sputtering deposition method. The photoelectrochemical performance was improved by adding various kinds and concentrations of alcohol, i.e., model compounds of biomass, to water. The separate evolution of pure H-2 was observed to proceed efficiently on these Vis-TiO2 thin films under visible light irradiation by using an aqueous solution of methanol.