A Ni-catalyzed reductive dialkylation of 8-aminoquinoline-tethered aliphatic alkenes with two unactivated alkyl electrophiles is disclosed here. Key to the development of this transformation is the combination of primary alkyl (pseudo)halides and secondary alkyl iodides that produce products in a single regioselective manner. The reaction exhibits good functional group compatibility, and its synthetic utility was demonstrated by the concise synthesis of the precursors of biologically relevant molecules.