A family of highly emissive benzo[4,5]thiazolo[3,2- c][1,3,5,2]oxadiazaborinines, conjugated with the donor 4-dimethylaminophenyl group, was designed and synthesized. Their photophysical, both in solution and in the solid state, and structural properties were investigated. The influence of donor and acceptor substituents (R) in the benzothiazole unit on photophysical properties of complexes was found out. The tetrafluorobenzothiazole analogue exhibits nonbonded nuclear spin-spin coupling between fluorines from the BF2 group and α-fluorine atom at the benzene ring. Additionally, this boron complex demonstrates a comparatively high solid-state fluorescence quantum yield (Φ = 0.34).