A　new　hybrid　coordination　polymer　{[Cu(II)(2,2′-bipy)3][Pb2I6]}n　(1)　was　synthesized　by　the　reaction　of　Cu(NO3)2,　2,2′-bipy,　PbI2　and　NaI　in　DMF/DMSO　mixed　solvent.　As　revealed　by　X-ray　structural　analysis,　1　consists　of　[Pb2I6]n2n-　polyanions　and　discrete　[Cu(II)(2,2′-bipy)3]2+　structure-directing　agent　cations.　The　polymeric　negative　chain　[Pb2I6]n2-　is　built　up　by　face-sharing　of　PbI6　octahedra.　Structure-directing　reagent　cations　and　polymeric　negative　chains　are　in　combination　with　each　other　by　static　attracting　force　to　form　so-called　hybrid　structure.　Experimental　and　theoretical　optical　property　investigations　indicate　that　1　possesses　semiconductor　property.　DFT　calculation　was　executed　to　probe　the　electronic　structure　of　1.　To　our　interest,　when　using　both　second　metal　and　π　system　as　electronic　tuning　species,　conjugated　system　is　more　preferable.　©　Springer　Science+Business　Media,　LLC　2009.