Efficient blue phosphors remain as the formidable challenges for organic light‐emitting diodes (OLEDs). To circumvent this obstacle, a series of Ir(III) based carbene complexes bearing asymmetric di‐N‐aryl 6‐(trifluoromethyl)‐2H‐imidazo[4,5‐b]pyridin‐2‐ylidene chelates, namely, f‐ct6a ‒ c, were synthesized and their structures and photophysical properties were comprehensively investigated. Moreover, these emitters can undergo interconversion in refluxing 1,2,4‐trichlorobenzene, catalyzed by a mixture of sodium acetate (NaOAc) and p‐toluenesulfonic acid monohydrate (TsOH·H2O) without decomposition. All Ir(III) complexes present good photoluminescence quantum yield (ΦPL = 83 – 88%) with peak maximum (max.) at 443 ‒ 452 nm and narrowed full width at half maximum (FWHM = 66 – 73 nm). Among all fabricated OLED devices, f‐ct6b delivered a max. external quantum efficiency (EQE) of 23.4% and Commission Internationale de L'Eclairage CIE(x,y) coordinates of (0.14, 0.12), whereas the hyper‐OLED device based on f‐ct6a and 5H,9H,11H,15H‐[1,4] benzazaborino [2,3,4‐kl][1,4]benzazaborino[4′,3′,2′:4,5][1,4]benzazaborino[3,2‐b]phenazaborine‐7,13‐diamine, N7,N7,N13,N13,5,9,11,15‐octaphenyl (ν‐DABNA) exhibited max. EQE of 26.2% and CIE(x,y) of (0.12, 0.13). Finally, the corresponding tandem OLED with f‐ct6b as dopant gave a max. luminance of over 10000 cd⋅m‒2 and max. EQE of 42.1%, confirming their candidacies for making true‐blue OLEDs.This article is protected by copyright. All rights reserved