Two　new　heterometallic　inorganic-organic　hybrids　containing　polynuclear　halobismuthates　anions　and　ruthenium　complex　cations,　i.e.,　[Ru(tpy)(2)](2)[(Bi2I7Cl2)center　dot　I]　(1),　[Ru(bipy)(2)(bipyo](2)(Bi4I16)　(2),　(tpy　=　2,2＇:6＇,2aEuro(3)-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　center　dot　center　dot　center　dot　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.　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　center　dot　center　dot　center　dot　I　hydrogen　bonds　contribute　to　the　formation　of　a　3-D　network,　and　their　absorption　spectra　and　photoluminescence　have　also　been　discussed.