By the deaminative coupling reaction of α-aminoesters and α-aminoacetonitriles with thiols, a new strategy for the synthesis of α-thioaryl esters and nitriles is described, representing an example of converting C(sp3)-N into C(sp3)-S bonds. The substrates form diazo compounds in situ in the presence of NaNO2, and then a transition-metal-free S-H bond insertion reaction occurs with thiophenol derivatives. The method is simple in operation and post-treatment and has good universality. The corresponding thioethers were obtained in moderate to good (up to 90%) yields under mild conditions.