Uniform polystyrene (PS)/polypyrrole (PPy) composite microspheres with well-defined core/shell structures are synthesized by chemical oxidative polymerization. Gold nanoparticles (Au NPs) are successfully coated on the surface of PS/PPy microspheres by means of electrostatic interactions due to the functionalized PPy coatings supplying sufficient amino groups and the additive of mercapto acetic acid. Furthermore, the as-prepared PS/PPy/Au microspheres serving as seeds facilitate Au NPs further growth by in situ reduction in HAuCl4 solution to obtain PS/PPy/Au spheres with the core/shell/shell structure. Morphology observation demonstrates that the monodisperse PS/PPy/Au microspheres compose of uniform cores and the compact coatings containing distinct two layers. X-ray diffraction and X-ray photoelectron spectroscope confirm the existence of PPy and Au on the surface of the composite spheres. This facile approach to preparing metal-coated polymer spheres supplies the potential applications in biosensors, electronics and medical diagnosis. (C) 2015 Elsevier B.V. All rights reserved.