A　hybrid　iodoargentate　[(APHEN-H)2(Ag4I　6)]n　(1)　(APHEN　=　5-amino-1,10-phenanthroline)　has　been　obtained　by　the　routine　synthetic　reaction　and　structurally　determined.　In　1,　a　(Ag4I6)n2-　chain　was　defined　by　edge-sharing　of　Ag4I6　units,　and　its　quasi-three-dimensional　hybrid　structure　was　constructed　from　π-π　interactions　and　CHI　hydrogen　bonds.　Experimental　band　gap　of　about　2.30　eV　indicates　its　semiconductor　nature.　Strong　luminescence　can　be　detected　in　the　title　compound,　which　has　been　assigned　by　theoretical　calculation　with　DFT　method.　©　2010　Elsevier　B.V.　All　rights　reserved.