The thorium methyl and hydride complex (C5Me5)2ThMe2 and [(C5Me5)2Th(H)(μ-H)]2 catalyzed highly 1,2-regioselective dearomatization of pyridines via a hydroboration process is reported herein. Twelve different kinds of meta- and para-substituted pyridines are applicable to this reaction, giving the corresponding N-boryl-1,2-dihydropyridine products in high yields. Other N-heteroaromatic compounds, such as benzo-fused N-heterocycles, pyrazines, pyrimidines, 1,3,5-triazine, and benzothiazole, were also found to be hydroborated with high chemoselectivity. Kinetics including isotope effect studies revealed a first-order dependence on the concentration of catalyst, pyridine, and pinacolborane, with release of the dearomatized final product as the rate-determining step. A plausible mechanism is proposed on the basis of stoichiometric reactions and kinetic studies.