In this paper, we propose a general template synthesis approach towards composite hollow spheres using sulfonated polystyrene gel hollow spheres. The gel hollow spheres are highly crosslinked to well preserve the spherical contour during template synthesis. It is important that the gel shell is infiltrative to many species to allow their further growth therein by specific interaction. The grown materials are well distributed thorough the whole shell forming composite shells. This method is general, which is proved by the growth of many representative materials for example metal Pd nanoparticles, magnetite Fe3O4 nanocrystallites, conducting polyaniline, and inorganic fitania and silica. It is found that mesoporous inorganic shells are obtained after the template gel is calcined. This concept can be applied to other gel shells and grown materials expecting a new family of composite hollow spheres. (c) 2006 Published by Elsevier Ltd.