One-shot double, triple, and quadruple borylation reactions of triarylamines were developed through a judicious choice of boron source and Brønsted base. With the aid of borylation reactions, a variety of BN-doped nanographenes were synthesized in two steps from commercially available starting materials. An organic light-emitting diode device employing BN-doped nanographene as an emitter exhibited deep pure-blue emission at 460 nm, with CIE coordinates of (0.13, 0.11), and an external quantum efficiency of 18.3%.