A series of carbon xerogels-TiO₂ samples was prepared by sol-gel synthesis, modifying the synthesis procedure to have carbon-TiO₂ composite or TiO₂-coated materials. Textural, morphological and chemical properties were extensively characterized and correlated with the photocatalytic activity. In the case of composites, a homogeneous and highly mesoporous structure is formed, where the intimate contact between both phases allows a high and homogeneous dispersion of TiO₂ nanoparticles. During carbonization, the formation of oxygen vacancies is favoured, but the transition anatase to rutile is avoided by the carbon matrix. In the case of coated samples, microporous materials structured as microspheres were obtained, TiO₂ present a greater crystal size and some transformation to rutile. The synergetic role of carbon phase and the formation of oxygen vacancies in the TiO₂-phase contribute to narrow the composite band gap in such a manner that all samples are active under visible radiation reaching the total mineralization of the pollutant and the elimination of the toxicity.