Gamma radiolysis method was used to prepare polyvinyl alcohol (PVA) capped silver nanoparticles by optimizing various conditions like metal ion concentration and polymer (PVA) of different molecular weights. The role of different scavengers was also studied. The decrease in particle size was observed with increase in the molecular weight of capping agent. γ-radiolytic method provides silver nanoparticles in fully reduced and highly pure state. XRD (X-ray diffraction) technique confirmed the zero valent state of silver. Optical studies were done using UV-visible spectrophotometer to see the variation of electronic structure of the metal sol. Transmission Electron Microscopic (TEM) studies reveal the fcc geometry. The TEM show clearly split Debye-Scherrer rings. The d values calculated from the diffraction ring pattern are in perfect agreement with the ASTM data. Ag particles less than 10 nm are spherical in shape, whereas the particles above 30 nm have structure of pentagonal biprisms or decahedra, referred to as multiply twinned particles.