Hollow TiO2 structures have been synthesized on a large scale in H2O2 aqueous solution by a simple hydrothermal method. The morphologies and crystal Structures of hollow TiO2 structures can be controlled by titanium sources. Hollow anatase TiO2 microspheres composed of nanoparticles are prepared using titanium powder as titanium Source. With the pH value increased, TiO2 nanoparticles and cuboids with cylindrical hollow interiors are formed, respectively. However, hollow rutile TiO2 microspheres comprising radially aligned nanorods are fabricated using TiCl3 as titanium source. (C) 2008 Elsevier Ltd. All rights reserved.