We report a series of cyanide-bridged, heterodinuclear iridium(III) ruthenium(II) complexes with the generalized formula [Ir((R-2)(2)-ppy)2(CN)(ii-CN)Ru(bpy)(tpy-R-1)PF6 (ppy = 2-phenylpyridine, bpy = 2,2'-bipyridine, and tpy = 2,2':6',2"-terpyridine). The structural, spectroscopic, and electrochemical properties were analyzed in the context of variation of the electron-withdrawing (e.g., F, Br, CHO) and-donating (e.g., Me) and extended g-conjugated groups at several positions. In total, ten dinuclear complexes and the appropriate model complexes have been prepared. The iridium(III)-based emission is almost fully quenched in these complexes, and only the ruthenium(II)-based emission is observed, which indicates an efficient energy transfer toward the Ru center. Upon oxidation of the Ru center, the fluorinated complexes 2 exhibit a broad intervalence charge-transfer transition in the near-infrared region. The complexes are assigned to a weakly coupled class II system according to the Robin Day classification. The electronic structure was evaluated by density functional theory (DFT) and time-dependent DFT calculations to corroborate the experimental data.