TiO2 thin films were prepared on electrochemically etched porous Si by anodic oxidative hydrolysis of TiCl3 for the purpose of solar cell application. We compared electrochemical and photoelectrochemical properties of the TiO2-deposited porous Si electrodes (TiO2/porous Si) with those of a porous Si electrode. The TiO2/porous Si showed prolonged stability of photoluminescence and enhancements of photovoltage and photocurrent by 0.13 V and 67% increase, respectively, in comparison with porous Si due to the reduction of surface traps for charge carriers in the presence of TiO2 thin layer. Li+ and Na+ ions exhibited intercalation and deintercalation through the electrodeposited TiO2 film.