Until now, thermally activated delayed fluorescence (TADF) materials based on bridged boron-based acceptors have been primarily developed as dopants. However, in this study, we synthesized and characterized multifunctional deep-blue TADF materialst-OBO-DMAC and t-OBO-DPACusing bridged boron-based acceptors in combination with dimethylacridine or diphenylacridine as donors. These materials serve as both dopants and hosts. Theoretical calculations and experimentally measured photophysical properties of t-OBO-DMAC reveal a smaller singlet–triplet energy difference, higher photoluminescence quantum yield, and more efficient reverse intersystem crossing compared to t-OBO-DPAC. When evaluated as TADF emitters, t-OBO-DMAC and t-OBO-DPAC exhibited maximum external quantum efficiency (EQE) of 14.4 and 7.3% with deep-blue color coordinates of (0.14, 0.11) and (0.15, 0.07), respectively. Both materials were further assessed as hosts in various configurations, including host-only, TADF, phosphorescent, and phosphor-sensitized fluorescence (PSF)-emitting systems. Notably, t-OBO-DMAC demonstrated a high maximum EQE of 13.9% with deep-blue color coordinates of (0.15, 0.07) in a nondoped host-only device. Remarkably, both materials achieved EQEs exceeding 20% in the PSF devices. Our study marks a critical advancement in the field that breaks the conventional boundaries of the dopant and host and demonstrates unprecedented multifunctionalities for advanced organic light-emitting diodes.