A　hybrid　semiconductor　{[Cu(en)2][Pb2I　6]}n　(1)　(en　=　ethylenediamine)　templated　by　a　transition　metal　complex　was　synthesized　and　structurally　characterized.　The　title　compound　consists　of　discrete　structure-directing　molecules　(transition　metal　complex)　and　an　inorganic　iodoplumbate　polymer.　The　iodoplumbate　polymer　could　be　described　as　a　three-dimensional　network　constructed　from　a　[Pb　2I8]n4-　double　chain　bridged　by　iodine.　[Cu(en)2]2+　structure-directing　cations　are　discrete,　and　interact　with　the　inorganic　moiety　by　strong　static　attraction　and　the　H-bond　of　N　-　H•••I　to　give　a　so-called　hybrid　structure.　Experimental　and　theoretical　optical　property　investigations　indicate　that　1　possesses　semiconductor　properties.　A　density　functional　theory　calculation　was　executed　to　probe　the　regulation　effect　on　the　introduction　of　a　second　metal.　©　CSIRO　2008.