Electrogenerated radical-anions of 1,4-bis(alkylsulfonyl)benzenes can undergo two modes of reversible bond cleavage (depending on the stability of the alkyl radical) to afford alkylated monosulfones and phenolates, the latter of which can be trapped as ethers by reaction with electrophiles (alkyl iodides). For starting materials with primary and secondary alkyl moieties, we propose that the initially formed radical-anions rearrange (via an electrophilic aryl radical) to give aryl sulfinate radical-anions which decompose to yield phenolates and alkyl radicals.