Photocatalysts based on titanium dioxide have been prepared by a modified sot-gel process using different alkoxide precursors. Depending on the precursor and the calcination temperature of the gels, carbon-containing catalysts with large surface areas, capable to photodegrade p-chlorophenol (4CP) with visible light (lambda > 400 nm), have been obtained. Photodegradation and mineralisation were confirmed by HPLC and TOC measurements. The catalysts were characterised by physisorption of argon, elemental analysis, EPR, UV/VIS, X-ray powder diffraction (XRD), FT-IR and high-resolution transmission electron microscopy (HRTEM). A highly condensed, carbonaceous species formed during calcination is responsible for the photosensitisation. When used as a photoelectrode, the appearance of a photocurrent indicated the semiconductor nature of these novel materials. The catalysts exhibit a surprisingly good long-time stability despite of the carbonaceous nature of the sensitising species. It is also shown, that commercially available TiO2 can be photosensitised by impregnation with suitable alcohols followed by pyrolysis. (C) 2001 Elsevier Science B.V All rights reserved.