The film electrodes of TiO2, which have two functions of opto-electric conversion and storage of electrochemical energy, were prepared by pulsed laser deposition. To investigate the relationship between the photo-rechargeability and the surface structure, the TiO2 film electrodes with different surface morphology were prepared by changing the inert gas pressure during the deposition. The photo-charged quantity was found to be proportional to the third power of the rms of surface roughness. The results suggest that not only the surface but also the interstices between crystal grains near the surface contribute to the photo-charging with low photo-emf. (C) 2004 Elsevier B.V. All rights reserved.