TiO2 pillared clay materials were prepared by montmorillonite (Mt) and acidic solutions of hydrolyzed Ti alkoxides in the presence of high-molecular-weight polyoxypropylene (POP)-backboned di-quaternary salts (POP). The as-prepared materials were characterized by means of XRD, FTIR, TG-DTA, XRF, specific surface area and porosity determinations, TEM and SEM, respectively. The experiments showed that the resulting material was a porous delaminated structure containing pillared fragments and nano-scaled TiO2 particles well dispersed among each other. Introducing polymer surfactant POP as an expanding agent of Mt cannot only promote the formation of the delaminated structure, but significantly improve the porosity and surface area of the composites. The resulting TiO2 pillared Mt exhibited a good thermal stability as indicated by its surface area after calcination at 800 degrees C. No phase transformation from anatase to rutile was observed even under calcination at 900 degrees C. The grain size of anatase in as-prepared sample decreased with the increase of the POP concentration, but increased with the increment of calcination temperature. The photocatalytic performances of these new porous materials were evaluated by using methylene blue degradation. The composite solid exhibited superior photocatalyic property and the maximum removal efficiency was up to 98% within 90 min. (C) 2012 Elsevier B.V. All rights reserved.