Novel mixed-ligand Ir(III) complexes, [Ir(L)(NwedgeC)X]n+ (L = N/\C/\N or N/\N/\N; X = Cl, Br, I, CN, CH3CN, or -CCPh; n = 0 or 1), were synthesized, where N/\CwedgeN = bis(N-methylbenzimidazolyl)benzene (Mebib) and bis(N-phenylbenzimidazolyl)benzene (Phbib), N/\N/\N = bis(N-methylbenzimidazolyl)pyridine (Mebip), and N/\C = phenylpyridine (ppy) derivatives. The X-ray crystal structures of [Ir(Phbib)(ppy)Cl] and [Ir(Mebib)(mppy)Cl] [mppy = 5-methyl-2-(2'-pyridyl)phenyl] indicate that the nitrogen atom of the ppy ligand is located trans to the coordinating carbon atom in Me- or Phbib, while the coordinating carbon atom in ppy occupies the trans position of Cl. [Ir(Mebip)(ppy)Cl]+ showed a quasireversible Ir(III/IV) oxidation wave at +1.05 V, while the Ir complexes, [Ir(Mebib)(ppy)Cl], were oxidized at +0.42 V versus Fc/Fc+. The introduction of an Ir-C bond in [Ir(Mebib)(ppy)Cl] induces a large potential shift of 0.63 V in a negative direction. Further, the oxidation potential of [Ir(Mebib)(Rppy)X] was altered by the substitution of R, R', and X groups. Compared to the oxidation potential, the first reduction potential revealed an almost constant value at -2.36 to -2.46 V for [Ir(L)(ppy)Cl] (L = Mebib and Phbib) and -1.52 V for [Ir(Mebip)(ppy)Cl. The UV-vis spectra of [Ir(Mebib)(R-ppy)X] show a clear singlet metal-to-ligand charge-transfer transition around 407 approximately 425 nm and a triplet metal-to-ligand charge-transfer transition at 498 approximately 523 nm. [Ir(Mebip)(ppy)Cl]+ emits at 610 nm with a luminescent quantum yield of Phi = 0.16 at room temperature. The phosphorescence of [Ir(Mebib)(ppy)X] was observed at 526 nm for X = CN and 555 nm for X = Cl with the high luminescent quantum yields, Phi = 0.77 approximately 0.86, at room temperature. [Ir(Phbib)(ppy)Cl] shows the emission at 559 nm with a luminescent quantum yield of Phi = 0.95, which is an unprecedentedly high value compared to those of other emissive metal complexes. Compared to the luminescent quantum yields of the Ir(ppy)2(L) derivatives and [Ir(Mebip)(ppy)Cl]+, the neutral Ir complexes, [Ir(L)(R-ppy)X] (L = Me- or Phbib), reveal very high quantum yields and large radiative rate constants (kr) ranging from 3.4 x 10(5) to 5.5 x 10(5) s(-1). The density functional theory calculation suggests that these Ir complexes possess dominantly metal-to-ligand charge-transfer and halide-to-ligand charge-transfer excited states. The mechanism for a high phosphorescence yield in [Ir(bib)(ppy)X] is discussed herein from the perspective of the theoretical consideration of radiative rate constants using perturbation theory and a one-center spin-orbit coupling approximation.