We report a combined experimental and theoretical study on cationic Ir(III) complexes for OLED applications and describe a strategy to tune the phosphorescence wavelength and to enhance the emission quantum yields for this class of compounds. This is achieved by modulating the electronic structure and the excited states of the complexes by selective ligand functionalization. In particular, we report the synthesis, electrochemical characterization, and photophysical properties of a new cationic Ir(III) complex, [Ir(2,4-difluorophenylpyridine)2(4,4'-dimethylamino-2,2'-bipyridine)](PF(6)) (N969), and compare the results with those reported for the analogous [Ir(2-phenylpyridine)2(4,4'-dimethylamino-2,2'-bipyridine)](PF(6)) (N926) and for the prototype [Ir(2-phenylpyridine)2(4,4'-tert-butyl-2,2'-bipyridine)](PF(6)) complex, hereafter labeled N925. The three complexes allow us to explore the (C/\N) and (N/\N) ligand functionalization: considering N925 as a reference, we investigate in N926 the effect of electron-releasing substituents on the bipyridine ligand, while in N969, we investigate the combined effect of electron-releasing substituents on the bipyridine ligand and the effect of electron-withdrawing substituents on the phenylpyridine ligands. For N969 we obtain blue-green emission at 463 nm with unprecedented high quantum yield of 85% in acetonitrile solution at room temperature. To gain insight into the factors responsible for the emission color change and the different quantum yields, we perform DFT and TDDFT calculations on the ground and excited states of the three complexes, characterizing the excited-state geometries and including solvation effects on the calculation of the excited states. This computational procedure allows us to provide a detailed assignment of the excited states involved in the absorption and emission processes and to rationalize the factors determining the efficiency of radiative and nonradiative deactivation pathways in the investigated complexes. This work represents an example of electronic structure-driven tuning of the excited-state properties, thus opening the way to a combined theoretical and experimental strategy for the design of new iridium(III) phosphors with specific target characteristics.