Preparation of nanocomposite kaolinite/TiO2, using hydrolysis of titanyl sulfate in the presence of kaolin was addressed. A variable (kaolin)/(titanyl sulfate) ratio has been used in order to achieve the desired TiO2 content in prepared nanocomposites. Calcination of the composites at 600 degrees C led to the transformation of the kaolinite to metakaolinite and to origination of metakaolinite/TiO2 composites. The prepared samples were investigated using X-ray fluorescence spectroscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy. thermogravimetry and diffuse reflectance spectroscopy in the UV-VIS region. Structural ordering of TiO2 on the kaolinite particle surface was modeled using empirical force field atomistic simulations in the Material Studio modeling environment. Photodegradation activity of the composites prepared was evaluated by the discoloration of Acid Orange 7 aqueous solution. (C) 2011 Elsevier B.V. All rights reserved.