A nickel catalyzed cross‐coupling protocol for the straightforward C−S bond formation has been developed. Various mercaptans and a wide range of ester and amide substrates bearing various substituents were tolerated in this process which afforded products in good to excellent yields. Furthermore, an intramolecular protocol for the synthesis of thioethers starting from thioesters has been developed. The utility of this protocol has been demonstrated in a new synthetic protocol of benzothiophene. A nickel catalyzed cross‐coupling protocol for facile C−S bond formation was developed. Various thiols and a wide range of ester and amide substrates bearing various substituents were tolerated in this process which afforded products in good to excellent yields. An intramolecular protocol for the synthesis of thioethers starting from thioesters was also developed and its utility was demonstrated in the synthesis of benzothiophene on the bench top.