A direct electrooxidative sulfonylation/heteroarylation reaction of alkenes with sulfinic acids, which proceeds through distal heteroaryl ipso-migration and C-S and C-C bond formations, is reported. This electro-synthetic method offers an efficient and environmentally friendly entry to prepare various sulfonated functionalized heteroarenes under an undivided cell at room temperature, avoiding the use of any metal catalysts, additives, and oxidants. Preliminary mechanistic studies indicated a radical pathway.