Electrochemical reduction of p-nitrophenyl methyl sulfone (1) and p-cyanophenyl methyl sulfone (2) at mercury and platinum cathodes in dimethylformamide containing tetra-n-butylammonium tetrafluoroborate has been investigated. Electrogenerated radical anions of these compounds are long-lived and do not undergo classic two-electron cleavage of the aliphatic carbon-sulfur bond. Instead, due to the electron-withdrawing nitro and cyano substituents, other reactions occur. For 1, the principal product is p-nitrophenolate, which can he trapped as a p-nitrophenyl alkyl ether upon treatment with an alkyl iodide or which can be protonated to give p-nitrophenol. The radical anion of 2 can lose CN- or CH3SO2- to give radicals which couple to form 4,4'-dicyano-, 4,4'-bis(methanesulfonyl)-, and 4-cyano-4'-(methanesulfonyl)biphenyl; furthermore, when 1-iodobutane is added to an electrolyzed solution of 2, 1-butoxy-4-(methanesulfonyl)benzene results. These and other unexpected processes have been characterized by means of gas chromatography-mass spectrometry.