AbstractThis study proposes a novel approach to develop highly efficient, narrow‐emitting violet materials based on boron and oxygen polycyclic aromatic hydrocarbon multiple resonance structure. Herein, B‐2OCz is developed by fusing indole with a 5,9‐dioxa‐13bboranaphtho[3,2,1‐de]anthracene (DOBNA) core to enhance its thermally activated delayed fluorescence (TADF) properties and molecular rigidity. On the other hand, the B‐2OCz‐Si is decorated with a bulky tetraphenylsilyl substituent. B‐2OCz‐Si exhibits exceptional features such as violet emission at 397 nm, a very small full width at half maximum of 16 nm, and 82% of photoluminescence quantum yield. The B‐2OCz‐Si devices achieve a high external quantum efficiency of over 15%, violet emission with a peak wavelength of 423 nm, and color coordinates of (0.156, 0.037). Furthermore, the B‐2OCz‐Si is used as an electron transport type host material for phosphorescent organic light‐emitting diodes (PhOLEDs), based on its high triplet energy and TADF properties. As compared to the conventional triazine based host materials, these newly developed DOBNA‐based materials display superior device lifetime performance. All these potential aspects corroborate that this new class of DOBNA‐based materials can work as a promising host material for PhOLEDs and violet‐emitting fluorescent devices.