Here, we report a nickel-catalyzed enantioconvergent hydroalkylation of olefins with trifluoromethyl-containing α-alkyl halides for the synthesis of enantioenriched trifluoromethylated alkanes. This reaction employs readily available and bench-stable alkenes as alkyl coupling partners, featuring mild conditions, a broad substrate scope, and high functional group tolerance. The synthetic utility of this method is further demonstrated in the late-stage functionalization of a range of drug molecules and natural products.