AbstractThe development of phosphorescent materials with ultrapure emission is of great significance for wide‐color‐gamut organic light‐emitting diodes (OLEDs). Herein, a ligand steric interlocking strategy is introduced to achieve the narrowband emission of phosphorescent Ir(III) complexes. The steric interlocking effect contributed by the short distance between ligands leads to enhanced rigidity, and suppresses the high‐frequency vibrations of oICz‐Ir. In this context, oICz‐Ir exhibits an ultrapure green phosphorescence with a small full width at half maximum (FWHM) of 23 nm peaking at 521 nm in solution. Furthermore, the oICz‐Ir‐based OLED achieves a maximum external quantum efficiency (EQEmax) of 18.9%, an excellent color purity with Commission Internationale de L'Eclairage coordinate y (CIEy) of 0.69, making it the purest green bottom‐emitting phosphorescent OLEDs. Meanwhile, with oICz‐Ir as the sensitizer, a phosphorescence sensitized fluorescent OLED shows an excellent EQEmax of 31.1% with the CIEy of 0.7.