Electrochemical oxidation of sulfinic acids has been studied in aqueous solutions using cyclic voltammetry, controlled-potential coulometry, chronoamperometry and chronocoulometry methods. The results indicate that the oxidation of sulfinic acids is an irreversible one-electron transfer process. Our data also show that the electrogenerated sulfonyl radicals undergo a dimerization reaction to form disulfone derivatives. The present work has led to the development of a facile and environmentally friendly electrochemical method for the synthesis of diphenyl disulfone derivatives.