The synthesis of rutile (TiO2) nanostructured materials at low temperature from TiCl4 aqueous solution was described. TiO2 coatings on polystyrene (PS) particles were prepared by layer-by-layer assembly technique. The samples were characterized by DTA-TG, SEM, XPS, TEM and XRD techniques. The experimental results showed that pure rutile-TiO2 coatings with nanocrystal structure were synthesized at 100 degrees C. On the surface of PS particles, sphere-type TiO2 coatings exhibited uniform shape and a narrow size distribution. The amount of TO2 (wt%) and shell thickness of particles increased with the adding of coating layers. Hollow TiO2 spheres were obtained by calcination at 450 degrees C. TiO2/PS with 2 coating layers showed higher degradation rate. The photocatalytic activity of hollow TiO2 spheres was higher than that of TiO2/PS.