A novel iron-catalyzed highly regioselective protoboration of alkenes on N-heterocycles, which constitute an important type of core in a variety of pharmaceutical compounds, has been developed. Under practical reaction conditions, a series of N-heterocycles each containing organoboride were accessed. Further synthetic experiments demonstrated that the products of this transformation could be used as versatile precursors to prepare complicated compounds. Moreover, a reaction mechanism was proposed based on control experiments.