A new method for immobilizing nano-scaled TiO2 on the surface of montmorillonite (Mt) clay has been developed. First, cationic surfactants were introduced into the Mt galleries through ion exchange and physical adsorption processes. Next a titanium precursor with negative charges was allowed to hydrolyze and condense around the nature clay to form meso-phase assemblies on the external and internal surface of the Mt. After the removal of the surfactant, a highly porous TiO2 pillared clay with mesopores was formed. The cationic surfactant has a templating role, which not only tailored the formation of TiO2 but also controlled the TiO2 content in the composite. The photocatalytic performances of these new porous materials were evaluated by using methylene blue degradation. The photocatalytic activity of these TiO2 composite is higher than that of P25 although TiO2 only accounts for about one-third of the sample's mass in the composite samples. (C) 2014 Elsevier B. V. All rights reserved.