Sol-gel SiO2/TiO2 and TiO2/SiO2 bi-layer films have been deposited from a polymeric SiO2 solution and either a polymeric TiO2 mother solution (MS) or a derived TiO2 crystalline suspension (CS). The chemical and structural properties of MS and CS bi-layer films heat-treated at 500 degrees C have been investigated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscospy. Water contact angle measurements show that MS SiO2/TiO2 and CS TiO2/SiO2 bi-layer films exhibit a natural superhydrophilicity, but cannot maintain a zero contact angle for a long time over film aging. In contrast, CS SiO2/TiO2 bi-layer films exhibit a natural, persistent, and regenerable superhydrophilicity without the need of UV light. Superhydrophilic properties of bi-layer films are discussed with respect to the nature of the TiO2 single-layer component and arrangement of the bi-layer structure, i.e. TiO2 underlayer or overlayer. (C) 2007 Elsevier B.V. All rights reserved.