Photo-induced hydrophilicity of SiO2/TiO2 multilayer film prepared by using the vacuum deposition method was investigated by means of water contact angle measurement. Using black light irradiation of the films centering at a wavelength of 365 nm, an extreme photo-induced hydrophilicity was achieved when the TiO2 film was covered by SiO2 overlayer ranging from 10 to 20 nm in thickness. These multilayer films exhibited much more extreme hydrophilicity than the TiO2 film without SiO2 overlayer. The surface analyses revealed that the enhanced photo-induced hydrophilic surface of the multilayer films exhibited an improved photo-catalytic activity towards decomposition of organic substances on their surfaces. It was found that significant growth of the SiOH group occurred in the uppermost surface of the SiO2 overlayer of the multilayer films through the depth profile measurement of TOF-SIMS. This result suggests that the photo-generated reactive species such as hole created in the TiO2 film may transmit the SiO2 layer to reach the surface. The enhanced photo-induced hydrophilicity of the films can be explained by a synergetic effect of the improved photo-catalytic activity of the multilayer film and the stable hydrophilicity of SiO2 itself.