The　electrochemical　synthesis　of　o-benzoquinones　and　their　in　situ　transformation　is　a　versatile　approach　for　the　synthesis　of　polyhydroxylated　aromatics.　In　the　present　paper,　the　electrochemical　oxidation　of　catechol　in　the　presence　of　ketene　N,S-acetals　as　N,C-doubly　nucleophiles　was　first　investigated　using　cyclic　voltammetry　technique.　Then　preparative　scale　of　electrolysis　was　carried　out　to　demonstrate　that　polyfunctionalized　indoles　could　be　one-pot　synthesized　under　constant　current　electrolysis　conditions.　Finally,　the　reaction　mechanism　was　proposed.