Silver nanoparticle/bis(o-phenolpropyl)silicone composites have been synthesized by the reduction of silver nitrate with bis(o-phenolpropyl)silicone BPPS [(o-phenolpropyl)2(SiMe2O)n, n = 2, 3, 8, 236]. TEM and FE-SEM data clearly show that the silver nanoparticles with the size of < 20 nm are well dispersed throughout the BPPS matrix in the composites. XRD patterns are consistent with those for multicrystalline silver. The size of silver nanoparticles increased with increasing the relative molar concentration of silver salts added. It was found that in the absence of BPPS, most of the silver nanoparticles undergo macroscopic precipitation by agglomeration, indicating that BPPS is essential to stabilize the silver nanoparticles.