The　hydrothermal　synthesis　and　structural　characterization　of　five　copper　iodides　derived　from　chelated　ligands,　1,　10-phenanthroline　(phen),　ethylenediamine　(en)　and　1,　3-propanediamine,　are　reported.　Except　monovalent　copper　compound　1　((phen)Cu3I3　1),　other　four　compounds　([Cu(phen)2I][CuI2]　2,　[Cu(phen)2I][Cu3I4]　3,　[Cu(en)2][Cu4(phen)2I6]　4　and　[Cu(1,　3-propanediamine)2][CuI2]2　5)　are　mixed-valent　Cu(I)-Cu(II)　compounds　by　partially　auto-oxidated　from　Cu(I).　Supramolecular　frameworks　of　these　compounds　can　be　assembled　by　C/N-HI　hydrogen　bonds,　Cu(I)-Cu(I)　interaction,　weak　Cu-I　semicoordinate　interaction,　C-Hπ　and　π-π　stacking　interactions.　It＇s　noteworthy　that　we　find　hydrothermal　synthesis　under　higher　pH　value,　higher　synthesis　temperature　and　longer　reaction　time　can　obtain　higher　ratio　of　Cu(I)/Cu(II)　copper　iodides　and　organic　ligand　with　lower　steric　hinderance　is　prone　to　coordinated　with　divalent　copper　to　form　cation　unit.　Finally,　the　fluorescent　study　shows　1　exhibits　intense　orange-red　luminescence　with　long　lifetime　at　293　K　and　more　intense　emission　and　longer　lifetime　at　77　K.　Moreover,　the　room　temperature　EPR　spectra　of　above　five　compounds　not　only　show　the　valence　of　copper　but　demonstrate　the　coordination　environment　of　Cu(II)　centre.　©　2008　Elsevier　Inc.　All　rights　reserved.