Thiolates are known as the inhibitors of metal catalysis due to their strong coordination with the metal. Herein, we reported visible-light-induced homolysis of the Ni-S bond to activate the nickel(II) thiolates for the C-S coupling, obviating the use of exogenous photocatalysts and other additives. Various aryl bromides/iodides can efficiently couple with thiols with a wide range of functional groups under mild conditions. Preliminary mechanistic studies suggested the homolysis of the Ni-S bond is the key step for couplings and nickel(0) is not involved in the process.