Amine functional polymeric spheres were prepared via the dispersion polymerization of 2-dimethylaminoethyl methacrylate and methylmethacrylate in supercritical carbon dioxide, and they were employed efficiently as templates for the fabrication of hollow silica particles. A small amount of divinyl benzene was used as a crosslinking agent to control the morphology of the copolymeric particles from clumpy solid to spherical shape. The assembly of the polymeric spheres with tetraethylorthosilicate (TEOS) through hydrothermal methods produced core-shell type hybrid particles. The whole process required neither surface treatment for the polymeric particles nor addition of any acidic or basic catalyst for the hydrolysis of silica precursor because dimethylamino groups of the copolymeric spheres were able to absorb water and catalyze the hydrolysis of TEOS for the deposition of the silica gel network. The polymeric cores were completely removed by calcination process and silica hollow particles with well-defined structure were obtained finally. The silica hollow particles were characterized by scanning electron microscopy and transmission electron microscopy, which clearly revealed that the silica spheres had the hollow structure with 151 nm wall thickness. (C) 2009 Elsevier B.V. All rights reserved.