A copper‐promoted thiolation of C(sp2)–H bonds with disulfides was achieved by using 2‐amino alkylbenzimidazole (MBIP amine) as a new and removable N,N‐bidentate directing group. This strategy gives a variety of functionalized thioethers in moderate to excellent yields in a simple and efficient way. Importantly, the substrate scope is not limited to aromatic amides; diverse alkenyl amides are also compatible. Furthermore, this synthetic approach provides a potentially feasible way to achieve structural modification of related benzimidazole‐containing compounds through direct C–H activation.