Eccentric double-shelled hollow polyethylacrylate (PEA)/polystyrene (PS) crosslinked composite spheres were synthesized by phase separation during swelling polymerization of their mother polymer hollow spheres. The group -NH2 was introduced within the network by ammonization of PEA. Other materials for example silica could be favorably grown within the gel network by a sol-gel process. The polymer/silica hollow spheres gave the corresponding derivative hollow spheres with varied composition including SiO2/carbon, carbon and beta-SiC, with the eccentric double-shelled morphology retained. (C) 2009 Elsevier Ltd. All rights reserved.