An　efficient　protocol　for　the　synthesis　of　thiosulfonates　via　the　electrochemical　oxidative　sulfonylation　of　thiols　and　sodium　sulfinates　has　been　developed.　The　electrochemical　oxidative　sulfonylation　reaction　proceeded　using　NH4I　both　as　a　redox　catalyst　and　a　supporting　electrolyte　in　undivided　cell　equipped　with　graphite　anode　and　graphite　cathode　under　constant　current　condition.　This　process　avoids　the　utilization　of　external　oxidants　or　corrosive　molecular　iodine　and　therefore　represents　an　environmentally　benign　means　for　achieving　the　transformation.