Comprehensive SummaryAlkenylsulfonates are commonly encountered in medicinal chemistry, polymer chemistry, and organic synthesis. In this research, an electrochemical reaction involving alkynes, NaHSO3, and alcohols has been developed. This method yields functionalized alkenylsulfonates in good yields with broad functional group tolerance. Mechanism studies indicate that anodic oxidation of inorganic sulfite, radical insertion process, and HAT process are involved in this transformation.