The intramolecular Csp3–H and/or C–C bond amination is very important in modern organic synthesis due to its efficiency in the construction of diversified N-heterocycles. Herein, we report a novel intramolecular cyclization of alkyl azides for the synthesis of cyclic imines and tertiary amines through selective Csp3–H and/or C–C bond cleavage. Two C–N single bonds or a CN double bond are efficiently