Two　iodoargentate　hybrids　templated　by　viologen　or　viologen-like　cations,　i.e.　[MV(AgI4)]n　(1)　and　[MBYP(AgI2)]n　(2),　(MV2+　=　methyl　viologen,　MBYP+　=　1-methyl-2,2′-　bipyridine)　have　been　synthesized　in　polar　organic　solvents.　(AgI4)]n　2-　and　(AgI2)]n　2-　chains　in　both　compounds　were　constructed　from　edge-sharing　of　normal　and　distorted　AgI4　tetrahedra,　and　a　2-D　supramolecular　layer　based　on　C-H···I　hydrogen　bond　was　observed　in　1.　The　band　gaps　of　1.54　and　2.67　eV　indicated　their　semiconductor　nature.　Their　band　gap　difference　was　led　by　different　hydrogen　bond　donors　in　MV2+　and　MBYP+,　which　result　in　more　diffused　p-π∗　antibonding　orbitals　in　MV2+.