Aiming at the high cost and complicated process for synthesizing block copolymers,the hydroxylated SBS (styrene-b-butadiene-b-stryene) was synthesized using home-made SBS through the macromolecular reaction route. The silver nanoparticles were prepared using the hydroxylated SBS (SBS-OH) as template,DMF (N,N-dimethylformamide) as solvent and AgNO3 as raw material under certain reaction conditions. The size and morphology of the silver nanoparticles were characterized using ultraviolet-visible absorption spectra and transmission electron microscope. The results show that the synthesized silver nanoparticles can offer the surface plasma characteristic absorption peaks possessed by nano-silver. The SBS-OH can act as a better template for the nucleation and growth of silver nanoparticles. And the synthesized silver nanoparticles have the spherical morphology and narrow size distribution.