The electrophilic borylation site of borylation reaction can be selectively controlled by varying the steric hindrance and electron-donating ability of the substrate substituent. The device based on the synthesized compound exhibits EQE of 21.6% with FWHM of 28 nm and CIE coordinates of (0.135, 0.094). The work provides an effective way for the development of high-performance MR-TADF emitter. • The electrophilic borylation site of one-shot electrophilic C–H borylation reaction can be selectively controlled. • New compounds tDPAC-BN and tDMAC-BN exhibited high PLQYs, narrow FWHMs, and satisfactory TADF properties. • The device based on tDPAC-BN achieved EQE of 21.6% with FWHM of 28 nm and CIE coordinates of (0.135, 0.094). Developing novel thermally activated delayed fluorescence (TADF) materials with a small full-width at half-maximum (FWHM) is very important for the fabrication of wide gamut and high-resolution displays of organic light-emitting diodes (OLEDs). In this work, we report two blue TADF emitters (tDPAC-BN and tDMAC-BN) with narrow FWHM based on a one-shot electrophilic C–H borylation reaction by selecting acridan-containing arylamine derivatives as the starting materials of borylation. The rigid skeleton structure significantly reduces vibrational motion, endowing tDPAC-BN and tDMAC-BN with high PLQYs (94.4% and 89.7%) and narrow FWHMs (19 nm and 26 nm in toluene). The electroluminescent devices employing tDPAC-BN and tDMAC-BN as emitters exhibit external quantum efficiency (EQE) of 21.6% and 22.3%, and CIE coordinates of (0.135, 0.094) and (0.116, 0.186), respectively. More importantly, we found the electrophilic borylation site of borylation reaction can be controlled by varying the steric hindrance effect and electron-donating ability of the substrate substituent. The different HOMO distribution originated from the differences in the substrate substituent accounts for different cyclization mode for tDPAC-BN and tDMAC-BN. Therefore, the work provides a useful strategy for broadening the range of high-performance TADF materials with narrow FWHM.