The first nickel-catalyzed thiolation of unactivated C(sp(3))-H bonds with disulfides was described. This transformation uses (dppp)NiCl2 as a catalyst and BINOL as a ligand, which are efficient for the thiolation of β-methyl C(sp(3))-H bonds of a broad range of aliphatic carboxamides. The reaction provides an efficient synthetic pathway to access diverse thioethers.