A microphase-separated, amphiphilic graft copolymer consisting of a poly (vinyl chloride) (PVC) backbone and poly(oxyethylene methacrylate) (POEM) side chains, (PVC-g-POEM at 62:38 wt %) was synthesized via atom transfer radical polymerization (ATRP). Nuclear magnetic resonance (H-1 NMR), FTIR spectroscopy, and transmission electron microscopy (TEM) clearly revealed that the "grafting from" method using ATRP was successful and that the graft copolymer molecularly self-assembled into discrete nanophase domains of continuous PVC and isolated POEM regions. The self-assembled graft copolymer film was used to template the growth of silver nanoparticles in solid state by introducing a AgCF3SO3 precursor and a UV irradiation process. The in situ formation of silver nanoparticles in the graft copolymer template film was confirmed by TEM, UV-visible spectroscopy, and wide angle X-ray scattering. FTIR spectroscopy and X-ray photoelectron spectroscopy also demonstrated the selective incorporation and in situ formation of silver nanoparticles within the hydrophilic POEM domains, presumably due to strong interactions between the silver and the ether oxygen in POEM. (c) 2008 Wiley Periodicals, Inc.