Polystyrene (core)-titania (shell) composite spheres consisting were readily prepared by a sol-gel process of titanium tetrabutoxide (TBOT) in a mixed solvent of ethanol/acetonitrile (3: 1, v/v). Smooth and homogeneous titania coatings formed when the mixed solvent was dehydrated by anhydrous sodium Sulfate. The thickness and surface roughness of titania coating increase with increase of the TBOT concentration. By adjusting the TBOT concentration in the range of 5.8-29.0 mM, the size of titania-coated PS spheres could be varied from 990 to 1125 nm. Calcination at elevated temperature gave dense, homogeneous, robust shells of anatase titania. The sizes of titania hollow spheres are 11.3-16.9% smaller than those of the titania-coated PS spheres as a result of calcination-induced shrinkage. The composite and hollow spheres were characterized by scanning electron microscopy, transmission electron Microscopy and electron diffraction measurements. These core-shell organic-inorganic spheres and hollow ceramic spheres may have wide applications in catalysts, adsorbents, lightweight fillers, capsules, etc. (C) 2009 Elsevier Ltd. All rights reserved.