The novel nanostructured F-containing TiO2 (F-TiO2) sphere was directly synthesized on the surface of Ti foil in the solution of NH4F and HCl by one-step hydrothermal approach under low-temperature condition. The samples were characterized respectively by means of field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The results showed that the F-TiO2 sphere was hierarchical structure, which composed of porous octahedron crystals with one truncated cone, leading to a football-like morphology. XPS results indicated that F anions were just physically adsorbed on the surface of TiO2 microspheres. The studies on the optical properties of the F-TiO2 were carried out by UV-vis light absorption spectrum. The surface fluorination of the spheres, the unique nanostructure induced accessible macropores or mesopores, and the increased light-harvesting abilities were crucial for the high photoelectrochemical activity of the synthesized F-TiO2 sphere for water-splitting. The photocurrent density of the F-TiO2 sphere thin film was more than two times than that of the P25 thin film. Meanwhile, a formation mechanism was briefly proposed. This approach could provide a facile method to synthesize F-TiO2 microsphere with a special morphology and hierarchical structure in large scale. (C) 2009 Elsevier B. V. All rights reserved.