1, 4-Bis (alkylsulfonyl) benzenes 2 exhibit the formation of a fairly stable anion radical under cathodic electron transfer. Its fragmentation leads both to 1-alkylsulfonyl-4-alkyl benzenes (ipso substitution) and 4-alkylsulfonylphenoxy ions, the presence of the latter suggesting a new mode of cleavage for strongly activated sulfones.