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.