Submicron scale particle aggregates with defined shape were prepared by self-assembling of sulphonated polystyrene latex particles Lit the interface of emulsion droplets. Several parameters were considered during the preparation, including the sulphonation time of the polystyrene latex particles, the composition of the oil phase, and the zeta potential of the sulphonated latex particle. To further improve the mechanical stability of the particle aggregates, a hard composite layer was formed by addition of melamine-formaldehyde (MF) prepolymer into the emulsion. The prepolymer was crosslinked onto the particles surface Of sulphonated PS particle aggregates. The crosslinking reaction was catalysed by the acidity of sulfogroup. After evaporating off solvent, PS/MF hollow microsphere composites were obtained as mechanically stable dry material. The hollow microsphere composite was characterized by TGA, FTIR. optical microscopy, scanning and transmission electron microscopy. (c) 2005 Elsevier Ltd. All rights reserved.