CONCLUSION

In summary, we have developed a structurally simplistic yet functionally superior D–A–D type UV emitter, D3CZ4F, through a one‐step coupling reaction. The molecule integrates an HLCT excited state with multiple intramolecular non‐covalent C–H⋯F locking interactions, which endow D3CZ4F with a remarkable oscillator strength of 1.3989 and an exceptional PLQY of 98% while effectively enabling triplet exciton utilization and UV emission. The non‐doped OLED achieved a maximum EQE of 7.33% with an EL peak at 390 nm and CIE coordinates of (0.164, 0.027). When doped in a CBP host, D3CZ4F maintained a high PLQY of 86%, and the corresponding device delivered a peak EQE of 8.97% at 388 nm, exhibiting minimal efficiency roll‐off (EQE of 8.15% at 500 cd m−2). This work confirms that the introduction of a non‐covalent locking strategy into UV molecular design can effectively enhance the photoelectric performance, which provides a molecular design paradigm for the development of high‐efficiency and low‐cost UV emitters and OLEDs.