An　electrochemically　regioselective　C-H　phosphorothiolation　of　(hetero)arenes　with　thiocyanate　as　the　S　source　under　ultrasonic　irradiation　has　been　developed.　The　synergistic　cooperation　of　electrooxidation　and　ultrasonication　markedly　accelerated　the　C-H　phosphorothiolation　reaction.　This　mechanistically　different　method　is　distinguished　by　its　wide　substrate　scope　and　transition-metal-free　and　external-oxidant-free　conditions,　thus　complementing　the　existing　metal-catalyzed　or　peroxide-mediated　protocols　for　the　green　synthesis　of　S-(hetero)aryl　phosphorothioates.