This work investigates the photocatalytic purification of water upon solar light over novel Ce-doped TiO2/clay heterostructures. These novel nanomaterials were prepared by a modified sol-gel route that allows, in a unique step, the formation of Ce-doped anatase nanoparticles and their assembling over an exfoliated clay material. Several synthesis parameters were optimized, including the anatase/clay ratio and the percentage of doping Ce incorporated. Remarkably enhanced activities toward the photodecomposition of several organic compounds were observed depending on the Ce and TiO2 contents. A synergistic effect has been observed among the textural properties, the amount of anatase formed and that of Ce doping. (C) 2015 Elsevier B.V. All rights reserved.