Hollow microspheres of mesoporous titania with a thin shell of anatase structure have been prepared by a simple procedure of surfactant poly(ethylene oxide) assisted nanoparticle assembly in nonaqueous system. A high surface area of 378 m(2)/g and pore volume of 0.34 cm(3)/g was obtained in the as-prepared sample with pore size of 2.6 nm. A large number of surface hydroxyl groups and a reduced band gap were found, which should be significant for multi-functionalisation of the surface and photocatalysis applications. A formation mechanism of hollow microspheres was proposed. (C) 2003 Elsevier Science B.V. All rights reserved.