We have demonstrated a general and facile method to synthesize composite hollow spheres by IPN-assisted transcription of polymeric hollow spheres. Starting from a parent PS hollow sphere, IPN polymer composite hollow spheres have been synthesized by a swell polymerization within the shell. The shell thickness and the cavity size are tunable by altering the feeding amount of the monomers. A variety of functional groups are derived by a selective modification of one network of the IPN polymer composite hollow spheres. By specific interactions of desired materials with gels, composite hollow spheres are obtained. The composition of the shell can be controlled within polymer, carbon, inorganic, metal and metallic compounds, and their composites. (c) 2008 Elsevier Ltd. All rights reserved.