Polyvinyl alcohol (PVA)/Ag hybrid nanocomposites have been prepared from polymeric film of PVA and silver nitrate (AgNO₃). The silver nanoparticles were generated in PVA matrix by the reduction of silver ions with gamma-irradiation. UV–visible spectra showed a single peak at 422 nm, arising from the surface plasmon absorption of silver nanoparticles. The shifting of surface plasmon resonance peak after irradiation reveals that the gamma irradiation can be used as a size controlling agent for the preparation of silver nanoparticles embedded in PVA film. This result was in good agreement with the result obtained from TEM images. The TEM images showed the narrow size distribution of the obtained Ag nanoparticles with average particle size of 30 nm, which decreased to 17 nm with increasing irradiation dose. The X-ray diffraction analysis revealed that silver metal was present in face centered cubic (fcc) crystal structure. These results clearly indicate that monodispersed silver nanoparticles are embedded homogenously in PVA matrix.