The catalytic dehydrogenative coupling of thiols with amines to produce desired sulfenamides and disulfides is an important catalytic reaction in industry. Presented herein is a protocol for the highly efficient electrochemical dehydrogenative coupling of thiols with amines/thiols to form S-N/S-S bonds, enabling the synthesis of S-N/S-S bonds under ambient conditions in the absence of oxidants, acids/bases or toxic (explosive) electrolytes, and the majority of the corresponding products are generated in yields of up to 99%. This protocol is believed to have great potential for industrial application.