Long live the OLED! Rational design and synthesis of IrIII complexes bearing two cyclometalated ligands (C N) and one 2‐(diphenylphosphino)phenolate chelate (P O) as well as the corresponding IrIII derivatives with only one (C N) ligand and two P O chelates are reported. According to the observed photophysical data, a P O ligand is found to be able to fine‐tune the light‐emitting electronic transition of these complexes.