A bulky organoborane (Ar2BMe)-B-F (Ar-F = 2,4,6-tris(trifluoromethyl)phenyl, 1) has been synthesized. In C6D6 solution this organoborane and pyridine form a frustrated Lewis pair. Under mild conditions, 1 can efficiently catalyze 1,4-hydroboration of a series of pyridines. This reaction is highly chemo- and regioselective. The reaction intermediate, a boronium complex [Py(2)Bpin][(Ar2B)-B-F(H)Me] (3), was characterized in solution by NMR spectroscopy, which was also confirmed by DFT calculation.