Inspired by these achievements, we sought to explore the influence of temperature on accurate and switchable site selectivity in alkene functionalization reactions. Herein, we report our discovery that switchable selectivity can be achieved in nickel-hydride-catalysed alkene migratory hydroalkylation (Figure ). Judicious selection of reaction temperatures led to protocols that provide the regiodivergent α-and β-C-H alkylation products and start from a single alkene substrate. 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. Furthermore, enantioenriched β-branched alkyl amines could be accessed in a catalytic asymmetric variant manner, which provides a convenient synthetic route to enantioenriched β-branched alkyl amines that are substantially important to the pharmaceutical chemistry and biochemistry fields (Figure ).