The bare n-TiO2 film electrode was found to be unstable during water splitting reactions under illumination of light. Significant improvement of stability was observed for Mn2O3 covered n-TiO2, i.e., n-TiO2/Mn2O3, thin film electrodes. The Mn2O3, layer also enhanced the rate of oxygen evolution instead of H2O2 formation, due to its catalytic effect. The highest photoresponse was found with an n-TiO2 film prepared at 850 degrees C for 13 min by thermal oxidation. The bandgap energy of both n-TiO2 and n-TiO2/Mn2O3 films was found to be 2.85 eV. X-ray diffraction results indicate rutile structure for the n-TiO2 film. The flatband potential of the n-TiO2 film was found to be -1.13 V/saturated calomel electrode from the intercept of the Mott-Schottky plot. The highest potential-assisted photoconversion efficiencies, 5.1 and 4.1%, and the corresponding practical photoconversion efficiencies, 2.0 and 1.6%, were obtained for water splitting by the n-TiO2 and n-TiO2/Mn2O3 film electrodes, respectively.