Three series of pentamethylcyclopentadienyl (Cp*) Ir(III) complexes with different bidentate ligands were synthesized and structurally characterized, [Cp*Ir(tpy)L] n+ (tpy = 2-tolylpyridinato; n = 0 or 1), [Cp*Ir(piq)L] n+ (piq = 1-phenylisoquinolinato; n = 0 or 1), and [Cp*Ir(bpy)L] m+ (bpy = 2,2'-bipyridine; m = 1 or 2), featuring a range of monodentate carbon-donor ligands within each series [L = 2,6-dimethylphenylisocyanide; 3,5-dimethylimidazol-2-ylidene (NHC); methyl)]. The spectroscopic and photophysical properties of these molecules and those of the photocatalyst [Cp*Ir(bpy)H]+ were examined to establish electronic structure-photophysical property relationships that engender productive photochemical reactivity of this hydride and its methyl analogue. The Ir(III) chromophores containing ancillary CNAr ligands exhibited features anticipated for predominantly ligand-centered (LC) excited states, and analogues bearing the NHC ancillary exhibited properties consistent with LC excited states containing a small admixture of metal-to-ligand charge-transfer (MLCT) character. However, the molecules featuring anionic and strongly σ-donating methyl or hydride ligands exhibited photophysical properties consistent with a high degree of CT character. Density functional theory calculations suggest that the lowest energy triplet states in these complexes are composed of a mixture of MLCT and ligand-to-ligand CT originating from both the Cp* and methyl or hydride ancillary ligands. The high degree of CT character in the triplet excited states of methyliridium complexes bearing C^N-cyclometalated ligands offer a striking contrast to the photophysical properties of pseudo-octahedral structures fac-Ir(C^N)3 or Ir(C^N)2(acac) that have lowest-energy triplet excited states characterized as primarily LC character with a more moderate MLCT admixture.