In this work, we report on the synthesis and characterization of six new iridium(III) complexes of the type [Ir(C<^>N)(2)(N<^>N)](+) using 2-phenylpyridine (C1-3) and its fluorinated derivative (C4-6) as cyclometalating ligands (C<^>N) and R-phenylimidazo(4,5-f)1,10-phenanthroline (R = H, CH3, F) as the ancillary ligand (N<^>N). These luminescent complexes have been fully characterized through optical and electrochemical studies. In solution, the C4-6 series exhibits quantum yields (& Fcy;) twice as high as the C1-3 series, exceeding 60% in dichloromethane and where (MLCT)-M-3/(LLCT)-L-3 and (LC)-L-3 emissions participate in the phenomenon. These complexes were employed in the active layer of light-emitting electrochemical cells (LECs). Device performance of maximum luminance values of up to 21.7 Lx at 14.7 V were observed for the C2 complex and long lifetimes for the C1-3 series. These values are counterintuitive to the quantum yields observed in solution. Thus, we established that the rigidity of the system and the structure of the solid matrix dramatically affect the electronic properties of the complex. This research contributes to understanding the effects of the modifications in the ancillary and cyclometalating ligands, the photophysics of the complexes, and their performance in LEC devices.