In this article, the microparticles of polystyrene-poly(styrene-co-sodium 4-styrenesulfonate) (PS-PSS) coated by polyaniline (PANI) were prepared and hollow PANI microspheres were further obtained by dissolving the core. First, surface-sulfonated monodispersed PS was prepared by copolymerization of sodium 4-styrenesulfonate (SSS) and styrene with dispersion polymerization method. Then aniline was polymerized on the surface of the surface-sulfonated PS (PS-PSS) by chemical oxidative polymerization. After purification, we prepared core-shell (PS-PSS)/PANI particles. Hollow PANI microspheres were prepared by dissolving the plastic PS core of the (PS-PSS)/PANI particles in chloroform. The growth process of PANI on the surface of PS-PSS particles was investigated and the hollow PANI microspheres were characterized. (c) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012