An intra-gallery template (IGT) method for synthesizing TiO2 pillared montmorillonite (coded as Ti-PILC) is set up. Different from the traditional routes, the IGT method does not need to prepare acidic colloidal titania, instead, the hydrolysis and condensation of titanium alkoxides take place in the interspaces of the montmorillonite, and thus the obtained Ti-PILCs have ordered mesoporous structure with big pillar height, and high photocatalytic activity. A series of novel Ti-PILCs with uniform pores but different pore sizes were synthesized, of which the dimension of the pores can be easily adjusted from 2.0 to 3.4 nm by changing the molecular length of the surfactant. With the presence of Ti-PILC, about 98% amount of methylene blue has been removed within 40 min, and the photocatalytic efficiency increases as the pore volume of Ti-PILC increases, suggesting that Ti-PILCs synthesized have great potential to be the photocatalyst for treating wastewaters. (c) 2013 Elsevier Ltd. All rights reserved.