The synthesis and characterization of spherical silver/polyphenylsilane (PPS) hybrid nanocomposites were carried out. A one-step conversion of metallic salts to stable metal nanoparticles was possible by a simple and mild PPS-mediated method. TEM (transmission electron microscopy) and FE-SEM (field emission scanning electron microscopy) data confirm the formation of the hybrid nanocomposites in which large numbers of silver nanoparticles (< 30 nm) are dispersed throughout the PPS matrix. XRD (X-ray diffraction) patterns are consistent with that for fcc-typed silver. The size and processability of such nanoparticles depend on the metal to PPS ratio. The PPS with Si-H functionalities play an important role as a reducing agent and as a stabilizing agent in the formation of the silver nanostructures. In the absence of the polymer, most of the silver particles underwent macroscopic precipitation.