AbstractMolecular phosphorescent heteroleptic bis‐tridentate iridium(III) emitters have been prepared via η1‐arene intermediates. In the presence of 4.0 mol of AgOTf, the complex [(IrCl{κ3‐N,C,N‐(pyC6HMe2py)})(μ‐Cl)]2 (1; pyC6H2Me2py=1,3‐di(2‐pyridyl)‐4,6‐dimethylbenzene) reacted with 9‐(6‐phenylpyridin‐2‐yl)‐9H‐carbazole (PhpyCzH) and 2‐phenoxy‐6‐phenylpyridine (PhpyOPh) to give [Ir{κ3‐N,C,N‐(pyC6HMe2py)}{κ3‐C,N,C′‐(C6H4pyCzH)}]OTf (2) and [Ir{κ3‐N,C,N‐(pyC6HMe2py)}{κ3‐C,N,C′‐(C6H4pyOPh)}]OTf (3). The X‐ray diffraction structures of 2 and 3 reveal that the carbazolyl and phenoxy substituents of the C,N,C′ ligand coordinate to the metal center to form an η1‐arene π bond. Treatment of 2 and 3 with KOtBu led to the deprotonation of the coordinated carbon atom of the η1‐arene group to afford the molecular phosphorescent [5t+4t′] heteroleptic iridium(III) complexes [Ir{κ3‐N,C,N‐(pyC6HMe2py)}{κ3‐C,N,C′‐(C6H4pyCz)}] (4) and [Ir{κ3‐N,C,N‐(pyC6HMe2py)}{κ3‐C,N,C′‐(C6H4pyOC6H4)}] (5). These complexes are green emitters that display short lifetimes and high quantum yields of 0.73 (4) and 0.87 (5) in the solid state.