Recently, it was reported that cyclometalated iridium(III) complexes of 2-((E)-2-phenyl-1-ethenyl)quinoline (PEQ) and 1-((E)-2-phenyt-1-ethenyl)isoquinoline (PEIQ) emitted saturated red light with high quantum efficiency and brightness. However, the energy difference between specific wavelengths due to the metal-to-ligand charge transfer ((MLCT)-M-3) absorption and emission spectra showed rather large Stokes shifts, which originated at the predominant (3)(pi-pi*) ligand-based emission. In this paper, it is shown that these complexes are consistent with predominant (3)(pi-pi*) ligand-based emission. To develop the predominant 3 MLCT emission of Ir complexes for a highly efficient phosphorescent complex suitable for red OLED devices, proper ligands having a highest occupied molecular orbital (HOMO) energy level similar to that of 2-phenylpyridine (ppy) ligand were designed to lead to strong mixing between pi-orbitals of ligands and the 5d orbital of the centric iridium atom. In order to decrease the HOMO energy level and the lowest an occupied molecular orbital (LUMO) level simultaneously to maintain the same HOMO-LUMO energy gap, an electron accepting group such as F or CF3 was introduced. By such manipulation of ligands in It complexes, it was theoretically possible to change the origin of emission in Ir complex from the predominant ligand-centered (3)(pi-pi*) excited state to the predominant 3 MLCT excited state. (C) 2006 Elsevier B.V. All rights reserved.