The purephase TiO₂ nanomaterials were synthesized by an autoclaving treatment of TiCl₄ with butanol as a single alcohol source. It was found that the control of molar ratio of TiCl₄ to butanol played an important role in determining the TiO₂ crystal phase and morphology. A highmolar ratio of TiCl₄ to butanol favored the formation of anat ase nanopart icles, whereas rutile nanorods were selectively obt ained at a lowmolar ratio of TiCl₄ to butanol. The morphology and structure of TiO₂ nanoparticles were characterized by X-ray diffraction, Raman microscope, and transmission electron microscopy and brunauer-emmet-tteller surface area analysis. Evaluation of the photocat alytic activity of the synthesized TiO₂ was performed in terms of decomposition of organic dyerhodamine Bunder ultraviolet irradiation. It turned out that the as synthesized TiO₂ crystallites possessed higher photocatalytic activities toward bleaching rhdomine B than deg ussa P25, benefiting from their high surface area, small crystal size as well as high crystallinity.