We report the electrochemical oxidation of rutin in acetonitrile-sodium phosphate (4:1 (v/v); pH 2.0) in the presence of p-toluenesulfinic acid. Cyclic voltammetry and controlled potential electrolysis were used to study rutin electro-oxidation and to prepare the sulfone derivatives. Chromatographic methods were employed to separate the products and IR, H-1 NMR, C-13 NMR, MS and microanalysis to their characterization. Data from cyclic voltammetry allow the identification of three rutin oxidation processes in the presence of p-toluenesulfinic acid (E-p(I) = 0.56 V, E-p(II) = 0.81 V and E-p(III) = 1.32 V). Only the electrode process around peak I was exhaustively studied. The first oxidation step leads to the formation of the corresponding o-quinone, which participates in a Michael addition reaction with the p-toluenesulfinic acid, forming the 6'(4-methylphenylsulfonyl)rutin and 6'(4-methylphenylsulfonyl)quercetin as majority products.