Silver nanostructured particles with controlled size, shape, and morphology were achieved by gamma irradiation of aqueous solution containing AgNO3, ploy (vinyl pyrrolidone), (PVP) or mixture of PVP and ploy (vinyl alcohol), (PVA). The reaction condition parameters such as solvent content, polymer type and irradiation dose were investigated. The physico‐chemical properties and morphological structures of the as‐prepared sliver nanostructures were characterized using UV/VIS spectroscopy, TEM, XRD, and Fourier transform infrared spectroscopy (FTIR) spectroscopy. Hexagonal and nanorods structures of sliver nanoparticles having single surface plasmon resonance peak and triangular (nanoprism) nanoparticles having different surface plasmon resonance peak were obtained. The XRD patterns of the as‐prepared silver nanostructure show four diffraction peaks at 2θ of 38.4°, 44.5°, 64.6°, and 77.6° of the face‐centered cubic structure silver nanoparticles. FTIR measurements indicated that the sliver nanoparticles were coordinated through the functional groups of PVA and/or PVP. POLYM. COMPOS., 38:2687–2694, 2017. © 2015 Society of Plastics Engineers