Poly(vinylpyrrolidone) (PVP)-capped copper nanoparticles synthesized by solvent-based polyol reduction were found to be effective catalysts for the polymerization of octadecylsilane and bis-(gamma-triethoxysilylpropyl)-tetrasulfide. Comparing with PVP-capped silver nanoparticles, copper nanoparticles exhibited different catalytic activity, and the polymerization products also showed different morphologies. The effects of transition metal ions on the polymerization of octadecylsilane catalyzed by PVP-capped silver nanoparticles were also investigated. It was found that transition of metal ions not only had strong effects on the morphologies of the products of polymerizations, but also resulted in the disappearance of silver oxide. The products were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) and X-ray powder diffraction (XRD). (C) 2009 Elsevier B.V. All rights reserved.