We successfully synthesized the TiO2/kaolinite (TiO2/Kao) composites with mixed phase TiO2 using a simple method at low temperature. The as-prepared TiO2/Kao composites were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), nitrogen adsorption/desorption measurements, Fourier transform infrared (FT-IR) spectroscopy and UV-vis diffuse reflectance spectra (DRS). The X-ray diffraction analysis indicated that the binary mixtures of anatase and rutile or the binary mixtures of anatase and brookite or the ternary mixtures of anatase, brookite, and rutile exist in the TiO2/Kao composites. The specific surface area of the TiO2/Kao composites is much higher than that of the kaolinite. The as-prepared samples exhibited strong photocatalytic activity for the removal of acid red G (ARC) and 4-nitrophenol (4-NP). The composites obtained at 70 degrees C showed the highest photocatalytic activity, in which the mixed phases of anatase and brookite existed. The high specific surface area and heterojunction microstructure could be responsible for the high photocatalytic activity. (C) 2011 Elsevier B.V. All rights reserved.