A facile and versatile method using a biopolymer as a chelating agent for silver ions and as a reducing agent for the formation of catalytic sites is proposed to prepare polystyrene (PS)/Ag core-shell microspheres. More specifically, the core-shell microspheres were fabricated by electroless plating after the formation of poly(dopamine)(PDA) on the surface of PS microspheres through in situ spontaneous oxidative polymerization of dopamine. The PS-PDA microspheres were characterized by SEM. XPS, and TGA. The results showed that a uniform PDA layer was formed on the PS microsphere surface and the thickness of the PDA layer could be well controlled by varying the concentration of dopamine solution. The PDA layer was used as a chelating agent for silver ions, as a reducing agent for the formation of catalytic sites by reducing the silver ions into silver nanoparticles, and as an adhesion layer between the PS microspheres and silver layer. SEM and XRD results indicate that the diameter of the silver nanoparticles decreased with the increase in the thickness of the PDA layer. The silver nanoparticles could form a continuous and compact silver layer on the surface of the PS microspheres. Furthermore, the PS-PDA/Ag core-shell microspheres showed a good conductivity of 10 S/cm and a low effective density of 1.8 g/cm(3), much lower than the corresponding values for block silver. Finally, hollow silver microspheres could be prepared by removing the PS core through calcination. SEM images showed that the hollow Ag microspheres remained unbroken and retained the spherical shape. (C) 2011 Elsevier Inc. All rights reserved.