A series of charge-neutral bis-tridentate Ir(III) complexes (1, 3, and 4) were prepared via employing three distinctive tridentate prochelates, that is, (pzp tB ph FO )H 2 , [(phpyim)H 2 •(PF 6 )], and [(pimb)H 3 •(PF 6 ) 2 ], which possess one dianionic pzp tB ph FO , together with a second monoanionic tridentate chelate, namely, (pzp tB ph FO )H, phpyim, and pimb, respectively. Moreover, a homoleptic, chargeneutral complex 2 was obtained by methylation of chelating (pzp tB ph FO )H of 1 in basic media, while closely related cationic complexes 5−7 were obtained by further methylation of the remaining pyrazolate unit of previously mentioned neutral complexes 2−4, followed by anion metatheses. All of these Ir(III) metal complexes showed a broadened emission profile with an onset at ∼450 nm, a result of an enlarged ligand-centered ππ* transition gap, but with distinct efficiencies ranging from 0.8% to nearly unity. Comprehensive spectroscopic and computational approaches were executed, providing a correlation for the emission efficiencies versus energy gaps and between the metal-to-ligand charge transfer/ππ* emitting excited state and upper-lying metal-centered dd quenching state. Furthermore, Ir(III) complexes 3 and 4 were selected as dopant emitters in the fabrication of sky-blue phosphorescent organic light-emitting diodes, affording maximum external quantum efficiencies of 16.7 and 14.6% with CIE x,y coordinates of (0.214, 0.454) and (0.191, 0.404) at a current density of 10 2 cd/m 2 , respectively. Hence, this research highlights an inherent character of bis-tridentate Ir(III) complexes in achieving high phosphorescence quantum yield at the molecular level.