In　this　paper,　an　inductively　coupled　plasma　(ICP)　enhanced　magnetron　sputtering　(MS)　method　was　utilized　to　deposit　silver　(Ag)　nanoparticles　embedded　inside　of　simultaneously　polymerized　poly(ethylene　oxide)　(PEO)　thin　film.　Ex　situ　transmission　electron　microscopy　(TEM),　selected　area　electron　diffraction　(SAED),　X-ray　photoelectron　spectroscopy　(XPS)　have　been　employed　to　elucidate　the　Ag　nanoparticle　structure,　shape,　and　growth　process　during　ICP　enhanced　MS　deposition.　The　results　showed　that,　when　capped　by　polymer　PEO　film,　the　Ag　nanocrystals　were　shaped　in　multiple-twinned　particles　(MTP)　and　further　transformed　into　decahedrons　held　five-twinning　structure　with　distinct　twinning　boundaries.　The　formation　of　particle　size　of　Ag　nanocrystalline　on　Si　(100)　surfaces　was　found　unambiguously　dependent　on　the　ICP　power,　and　the　estimated　particle　size　of　Ag　nanoparticles　was　in　the　range　of　5-10　nm.　From　the　results,　it　was　assumed　that　PEO　coating　was　the　reason　for　inducing　the,　formation　of　Ag　NITP　and　nanodecahedron　structures.