In the present study, electrochemical oxidation of 4-aminophenol (1a) has been studied in the presence of cyanoacetate derivatives 3a and 3b as nucleophile in a mixture of ethanol and phosphate buffer solution (0.15 M, pH 7) as green media using cyclic voltammetry and controlled-potential coulometry techniques. The obtained results indicate that the corresponding 4-iminocyclohexa-2,5-dienone (2a) formed from 4-aminophenol (1a) participates in the Michael addition reaction to yield new N- and O-heterocycles. The electrosynthesis of these new heterocycle compounds has been performed successfully in an undivided cell in good to excellent yields and high purity under mild conditions without any catalyst and toxic solvent.