Some new unsymmetrical diaryl sulfones were synthesized by anodic oxidation of fast violet B in aqueous/ethanol solutions in the presence of arylsulfinic acids at a carbon electrode. The data show that the electrogenerated N-acetyl-p-benzoquinone diimine was converted to the unsymmetrical diaryl sulfones by Michael type addition reaction with aryl sulfinic acids. This work has led to the development of a high yield, green, reagentless and facile electrochemical method for the synthesis of the described sulfones. In addition, four possible products were optimized at the BP86/def2-SVP level of theory by the parameters, natural charge, LUMO coefficient of Michael acceptor, thermodynamic and kinetic stability. (C) 2016 The Electrochemical Society. All rights reserved.