Efficient charge-transfer (CT) phosphorescence in the near-IR (NIR) spectral region is reported for four substituted Ru-(R-dipyrrinato) complexes, [Ru(bpy)(2) (R-dipy)](PF6), where bpy is 2,2'-bipyridine and the substituent R is phenyl (ph), 2,4,6-trimethylphenyl, 4-carboxyphenyl (HOOC-ph), or 4-pyridinyl. The experimentally determined phosphorescence efficiency, l(em(p)) = k(RA)(D(p))/(v(em(p)))(3) (where k(RAD(p)) and v(em(P)) are the phosphorescence rate constant and the phosphorescence frequency, respectively), of the [Ru(bpy)(2)(R-dipy)](+) complexes was approximately double that of [Ru(bpy)(Am)(4)](2+) complexes (Am = ammine ligand) in the NIR region. Density functional theory (DFT) modeling indicated two strikingly different electronic configurations of the triplet emitting state (T-e) in the two types of complexes. The T-e of [Ru(bpy)(2)(R-dipy)](+) complexes shows a CT-type corresponding to the metal-to-ligand charge transfer (MLCT)-(Ru-(R-dipy)) and the pi pi*-(R-dipy) moiety configurations, and the T-e state in the [Ru(bpy)(Am)(4)](2+) complexes corresponds to an approximately MLCT excited state consisting of mostly MLCT-(Ru-bpy) with a minimal pi pi*(bpy) contribution. DFT modeling also indicated that the low-energy singlet excited states in the T-e geometry (S-n(T)) of the [Ru(bpy)(2)(ph-dipy)](+) complex consist of numerous CT-S-n(T) -type states of the Ru-dipy and Ru-bpy moieties, whereas the [Ru(bpy)(Am)(4)](2+) ions show quite simple MLCT-S, (T) -type states of the Ru-bpy moiety. Based on experimental observations, DFT modeling, and the plain spin-orbit coupling (SOC) principle, we conclude that the remarkably high lem(p) amplitudes of the [Ru(bpy)(2)(R-dipy)](+) complexes relative to those of [Ru(bpy)(Am)(4)](2+) complexes can be attributed to the relatively substantial contribution of intrinsic SOC-mediated intensity stealing from the numerous low-energy CT-type S-n(T) states.