AbstractHighly efficient near‐infrared (NIR) emitters have significant applications in medical and optoelectronic fields, but the development stays a great challenge due to the energy gap law. Here, we report two NIR phosphorescent Ir(III) complexes which display emission peaks around 730 nm with a narrow full width at half maximum of only 43 nm. Therefore, pure NIR luminescence can be obtained without having a very long emission wavelength, thus alleviating the restriction of the energy gap law, and obtaining impressively high photoluminescence quantum yield up to 0.70. More importantly, the pure NIR organic light‐emitting diode (OLED) fabricated by the solution‐processed mothed shows outstanding device performance with the highest external quantum efficiency of 16.43 %, which sets a new record for solution‐processed NIR‐OLEDs based on different emitters. This work sheds light on the development of Ir(III) complexes with narrowband emissions as highly efficient pure NIR‐emitters.