An efficient oxidative thiolation of α-amino carbonyl compounds with thiols by the catalysis of an Earth-abundant nickel salt is disclosed for the first time. A variety of alkyl thiols and (hetero)aryl thiols underwent the reaction well with α-amino ketones and an α-amino ester to produce the desired α,α-aminothiocarbonyl compounds in good to excellent yields under ligand- and base-free conditions.