Triarylborane (Ar3B) and triarylamine (Ar3N) have been widely employed to construct electronically different donor-acceptor (D-A) systems. Herein, we describe a series of A-D-A-type luminescent organoboranes L-B2Nn (n = 1, 3, 5) that show an increased number of Ar3N units as electron donors and two terminal Ar3B as acceptors. When the Ar3N moieties were extended from one to five units, their electron-donating strength was gradually enhanced and the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps could also be tuned, which was further reflected in the red-shifted emissions from blue (λem = 458 nm) to orange (λem = 595 nm) with a decrease in Egap(elect) from 3.19 to 2.61 eV. L-B2N5 showed a huge Stokes shift (∼14 057 cm-1) and a considerably bright emission with an enhanced solid-state quantum efficiency (ΦS = 98%) compared with the other members. L-B2N3 and L-B2N5 exhibited aggregation-induced emissions (AIEs), and an apparent solvatochromic shift was also observed in the emission spectra as the solvent was changed from hexane to tetrahydrofuran (THF) (430 → 595 nm). In addition, the donor-acceptor charge-transfer character in these organoboranes caused a thermally responsive emission over a broad range.