Microspheres with silica as core and poly(4-vinylpyridine) (P4VP) as shell were synthesized. AuCl4 ions were bound by P4VP chains to form the complex, which acted both as an oxidant of pyrrole monomers and as a source of Au atoms. By vapor phase polymerization, the PPy and Au nanoparticles were simultaneously formed on the surfaces of SiO2@P4VP microspheres. The core-shell structure was confirmed by transmission electron microscopy. The surface morphologies of the composites were observed by scanning electron microscopy. The molecular structures of composites were characterized in detail by Raman spectra, X-ray diffraction, and X-ray photoelectron spectroscopy. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013