TiO2 films with controlled macroporous structures have been prepared from the precursor solution containing photo monomer pentaerythritol tetraacrylate by a photo polymerization-induced phase separation method (PIPS) in the absence of any surfactant and colloidal templates. The gel TiO2 film deposited from the precursor solution by dip-coating was irradiated with ultraviolet light for some time. During the irradiation process, the polymerization of the photo monomer was induced, which resulted in the phase separation in the film system. After the reaction, two phases existed in the film, one was the emerging polymer rich phase, another was the residual monomer-TiO2 oligomer rich phase. After heat-treatment at 600 degrees C, the entire polymer decomposed and a well-defined interconnected macroporous TiO2 films could be obtained. X-ray diffraction, scanning electron microscopy, atomic force microscopy, thermogravinnetric and differential thermal analysis were used to characterize the macroporous TiO2 films. The results showed that the macroporous texture could be tuned by changing the composition of the precursor solution. The solvent evaporation was controlled by the addition of polyvinylpyrrolidone. Highly macroporous TiO2 films prepared by the PIPS method exhibited much higher photocatalytic activity for the decomposition of methylene blue dye than the dense TiO2 film. (C) 2009 Elsevier B.V. All rights reserved.