The development of transition metal-catalyzed cross-coupling reactions, which enable to form carbon–carbon bonds has had a tremendous impact on many fields including organic chemistry, medicinal chemistry, materials science, and biology. Although the construction of carbon–carbon bonds between two sp2-hybridized carbons are relatively well established, cross-couplings of secondary alkyl electrophiles are still limited. Particularly, catalytic asymmetric cross-couplings of secondary alkyl electrophiles remain a challenge. In this seminar, the recent progress in the development of enantioselective syntheses of molecules possessing useful functional groups (e.g., nitriles, sulfones, sulfonamides, and boronate esters) at the stereogenic center via stereoconvergent cross-couplings using a chiral nickel catalyst will be presented. In addition, mechanistic studies to gain insight on the nickel-catalyzed asymmetric coupling reaction will be discussed.