Electrochemical oxidation of catechols ( 1a– e) has been studied in the presence of 2-acetylcyclopentanone ( 3) as a nucleophile in aqueous solutions, using cyclic voltammetry and controlled-potential coulometry. The results indicate that the quinones derived from catechols ( 1a– e), participate in Michael addition reactions with anion of 2-acetylcyclopentanone ( 3) and via EC mechanism pathway, converted to corresponding catechol derivatives ( 4a– e). In this work, we derived novel catechol derivatives with good yields based on electrochemical oxidation in aqueous solutions, at carbon electrode in an undivided cell, using environmentally friendly method.