Conjugated organoboranes with thermally activated delayed fluorescence (TADF) have emerged as a promising kind of organic emitting materials. In this study, we report the design of organoborane TADF emitters using double B←N bridged bipyridine (BNBP) as an electron-accepting unit. A series of novel BNBP-containing D‒A‒D-type organoboranes were facilely synthesized via the Buchwald–Hartwig amination and then borylation reactions. Their single-crystal and electronic structures, as well as photophysical and electrochemical properties were fully investigated. Notably, by varying the electron donor groups from diphenylamine and carbazole to 9,9-dimethyl-9,10-dihydroacridine, the slight overlapping between highest occupied molecular orbital and lowest unoccupied molecular orbital and small singlet-triplet energy gaps of organoborane molecule were obtained, thus leading to the intriguing TADF property. Moreover, the aggregation-induced emission characteristic was unexpected demonstrated for this organoborane molecule.