In drug discovery, the proportion of aliphatic carbons (C(sp(3))) and the presence of chiral carbons in organic molecules are positively correlated to their chance of clinical success. Although methods exist for the synthesis of chiral C(sp(3))-rich molecules, they often are limited in scope, have poor modularity or are unsuitable for stereoselective synthesis using racemic reagents. The stereocontrol of vicinal C(sp(3)) centres is a particular challenge. Here we describe nickel-catalysed enantio-and diastereoselective hydroalkylation of internal alkenes with racemic alkyl bromides to selectively form one of the four possible stereoisomers. Because of its general and modular character, and its high functional group tolerance, we expect this approach to have wide applications in the stereoselective synthesis of C(sp(3))-rich molecules.