We have studied the effective separation of photogenerated electrons and holes in the TiO2/VO2/TiO2 multilayer film electrodes prepared by a sputtering method, in which a very thin VO2 layer was inserted into the space charge layer of a TiO2 electrode. The photoelectrochemical properties, which were measured with a wet-type cell under white or visible light illumination, were largely dependent on the inserted position. A noticeably enhanced photogeneration was confirmed by inserting the thin VO2 layer of similar to2 nm in thickness at a position where the electric field gradient was considered to be large and by adjusting the Fermi level of the system to the 3d-levels of V4+. In addition, the formation of a very steep electric field was suggested even in the very thin film electrodes of similar to35-nm thick.