We disclose a temperature-regulated regiodivergent route for C(sp 3 )-C(sp 3 ) bond formation, a scarce phenomenon in transition-metal-catalysed organic synthesis. Regiodivergent alkylation was realized by varying only the reaction temperatures of alkene migratory hydroalkylation starting from the same raw materials, the identical alkene and alkyl halide substrates, using the same nickel-hydride catalytic system. This reaction also exhibits regioconvergence, delivering the predictable regioselective product with high regioselectivity from the arbitrary isomer or even isomeric mixtures of the alkene substrates. This protocol allows for the convenient synthesis of α-and β-branched alkyl amines, each of which are substantially important to the pharmaceutical chemistry and biochemistry fields. Detailed mechanistic studies revealed that, the formation of more stable nickelacycle provides the strong driving force of directional migration and the thermodynamic and kinetic