We synthesized a three-layer-type photocatalytic structure (TiO2/Cu(II)SiO2/SiO2), consisting of TiO2 on Cu(II)-grafted SiO2, which was deposited on a SiO2-coated glass substrate, and investigated its visible-light absorption and hydrophilic properties. Water contact angle measurements revealed visible-light-induced superhydrophilicity at the film surface that was initiated by interfacial electron transfer (IFET) at the interface of TiO2 and Cu(II)SiO2. Monitoring the oxidation state of Pb2+ ions confirmed that the IFET-initiated holes diffused to the TiO2 surface, where they likely contributed to the hydrophilic conversion. We also demonstrated that layer-structured TiO2/Cu(II)SiO2/SiO2 was stable under alkaline conditions. Thus, we successfully synthesized alkaline-resistant TiO2 that displays visible-light-induced superhydrophilicity.