The deposition of metallic oxides onto both single crystal and polycrystalline TiO2 electrodes using the photoelectrochemical technique was carried out, and the electrochemical behavior of the prepared PbO2/TiO2 electrode was studied. The photoelectrodeposition of PbO2, Fe2O3 and MnO2 occurred under illumination but not in the dark. The crystal orientation of the deposited oxides strongly depended on the crystal misfit between the oxides and the TiO2 substrate. Even pulse illumination brought about the deposition, because the OH radical produced on the surface by a hole significantly contributes to the oxide deposition during the initial step. The PEEG (photoelectrochemical epitaxial growth) model was proposed, and compared with the AFM images. From the measurements of the current-potential curve of the PbO2/TiO2 electrode, it was found that the PbO2 deposited on the polycrystalline TiO2 produces a surface state leading to a large anode tunneling current and that Fermi level pinning occurs at the PbO2/TiO2 interface. The present PbO2/polycrystalline TiO2 electrode was very stable in acidic solution, and therefore, will be very useful as an inert anode.