TiO2 with hierarchical architectures, tunable crystalline phase and thermal stability is successfully fabricated on a large scale through a facile hydrolysis process of TiCl4 combining with inducing of pollen. The structure of the as-prepared TiO2 is characterized by X-ray diffraction, Raman spectroscopy, infrared spectra, and scanning electron microscopy. The experimental results indicate that different phases (anatase, rutile or mixed crystallite) of TiO2 can be synthesized by controlling the experimental conditions. The pure phase of rutile or anatase can be obtained at 100 degrees C, while the pure phase of anatase can be retained after being annealed at 900 degrees C. The hierarchical structures TiO2 are constitute through self-assembly of nanoparticles or nanorods TiO2, which exhibit high and reused photo-catalytic properties for degradation of methylene blue. (C) 2011 Elsevier B.V. All rights reserved.