Abstract:　Two　new　heterometallic　inorganic–organic　hybrids　containing　polynuclear　halobismuthates　anions　and　ruthenium　complex　cations,　i.e.,　[Ru(tpy)2]2[(Bi2I7Cl2)·I]　(1),　[Ru(bipy)2(bipyo]2(Bi4I16)　(2),　(tpy = 2,2′:6′,2″-terpyridine,　bipy = 2,2′-bipyridine,　bipyo = 2,2′-bipyridine-6-olato)　have　been　structurally　determined.　These　hybrids　are　the　rare　examples　of　mixed-metal　halobismuthates　containing　photochemically　active　coordination　cations,　and　1　consists　of　mixed　halo　atoms.　C–H···I　hydrogen　bonds　among　halobismuthates　clusters　and　[Ru(tpy)2]2+/[Ru(bipy)2(bipyo]2+　countercations　contribute　to　the　formation　of　a　3-D　network.　Moreover,　their　absorption　spectra　and　photoluminescence　have　also　been　discussed,　and　their　absorption　edges　fall　in　the　range　of　those　of　semiconductors.　Graphical　Abstract:　Two　new　heterometallic　inorganic–organic　hybrids　containing　polynuclear　halobismuthates　anions　and　ruthenium　complex　cations　have　been　structurally　determined,　which　represent　the　rare　examples　of　mixed-metal　halobismuthates　containing　photochemically　active　coordination　cation　and　mixed　halo　atoms.　C–H···I　hydrogen　bonds　contribute　to　the　formation　of　a　3-D　network,　and　their　absorption　spectra　and　photoluminescence　have　also　been　discussed.[Figure　not　available:　see　fulltext.]　©　2015,　Springer　Science+Business　Media　New　York.