Two　new　types　of　iodoargentate/iodobismuthate-based　inorganic-organic　hybrids　were　prepared　and　structurally　characterized　as　{[Ln2(dpdo)(DMF)14](Ag12I18)}n　(bpdo　=　4,4′-bipyridine　N,N′-dioxide,　Ln　=　La　(1),　Nd　(2),　Sm　(3))　and　{[Ln(dpdo)(DMF)6](Bi2I9)2}n　(Ln　=　La　(4),　Pr　(5),　Er　(6)).　These　lanthanide-silver/bismuth　heterometallic　hybrids　feature　the　novel　templates　of　lanthanide-containing　metalloviologen　analogs,　i.e.,　[Ln2(dpdo)(DMF)14]6+　(dimers　for　1-3)　and　[Ln(dpdo)(DMF)6]n3n-　(1-D　chains　for　4-6).　The　(Ag12I18)n6n-　chains　in　1-3　are　constructed　from　edge-sharing　Ag6I12　units,　and　(Bi2I9)3-　clusters　in　4-6　are　defined　by　two　face-sharing　BiI6　otcahedra.　The　versatile　weak　interactions　between　metalloviologens　and　metal　iodides　stabilize　the　structures.　Upon　the　introduction　of　metalloviologens,　reversible　thermochromism　can　be　found　in　1-6.　Besides,　electrodes　with　films　of　1-6　exhibit　effective　and　repeatable　photocurrent　responses.　Finally,　the　possible　thermochromism　and　photocurrent　response　mechanisms　are　also　discussed.　©　2018　the　Partner　Organisations.