Effects of silver nanoparticles on the polymerization rate and morphology of poly(vinyl acetate) (PVAc)/silver microspheres prepared by suspension polymerization of VAc were investigated. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction and atomic absorption spectrometry were used to characterize the morphology and properties of the PVAc/silver microspheres. Due to the change of hydrophilicity of silver nanoparticles, appearance of the microspheres having golf ball-like convave surfaces was observed. Under controlled concentration of surfactant, PVAc/silver microspheres with various hollow structures were synthesized. In the case of silver nanoparticles modified by surfactant, the polymerization rate increased slightly. PVAc/silver microspheres with a conversion up to 80% were prepared via suspension polymerization.