An economical and practical azol-halogenation protocol of alkenes, which provides a general approach to construct a series of structurally diverse β-halogenated amine derivatives, is reported. The wide substrate scope, good functional group tolerance, ease of large-scale preparation and potential for product derivatization make this reaction attractive. Mechanistic studies suggest that the azol-halogenation process might involve a radical halogenation followed by nucleophilic azolyation.