Transition metal-loaded nanocrystalline SO42-/TiO2 powders were prepared by sol-gel method. Anatase is found as the active phase in all the samples. Sulfation process clearly stabilizes TiO2 catalyst phase against sintering, maintaining anatase phase and relatively high surface area values with respect to pure TiO2. Wide structural and surface characterization of samples was carried out in order to establish a correlation between the effect of sulfation and metal incorporation on the TiO2 photocatalytic properties. The maximum photocatalytic decomposition of methylene blue solution was achieved with sulfation of TiO2. In addition, incorporation of metal into the structure of SO42-/TiO2 seems to enhance the photocatalytic activity of the samples, which is ascribed to the enlargement of specific surface area, photogenerated carriers separation, light absorption, as well as the higher surface acidity. (C) 2010 Elsevier B.V. All rights reserved.