The formation of silver nanoparticle/bis(o-phenolpropyl)silicone composites have been promoted by the addition of chloroplatinic acid (<2 wt%) to the reaction of silver nitrate with bis(o-phenolpropyl)silicone BPPS [(o-phenolpropyl)2(SiMe2O)n, = 2, 3, 8, 236]. TEM and FE-SEM data exhibit that the silver nanoparticles having the size of <20 nm are well dispersed throughout the BPPS matrix in the composites. XRD patterns are consistent with those for polycrystalline silver. The addition of small amount of platinum to the silver accelerated the rate of composite formation by forming a Ag-Pt bimetallic alloy. The size of silver nanoparticles increased with increasing the relative molar concentration of silver salts added with respect to BPPS. However, the addition of platinum (1-5 wt%) to the AgNO3-BPPS mixture did not affect the size distribution of silver nanoparticles appreciably. 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 by coordination.