Electrochemical oxidation of tiron in the presence of H2O as a nucleophile in strongly acidic aqueous solutions was studied by cyclic voltammetry, controlled-voltage coulometry and spectrometric investigations. The mechanism of electrochemical reaction is confirmed by spectrophotometric tracing in various times of controlled-voltage coulometry. The voltammetric and spectrophotometric foundations indicate that a 1,4-Michael addition of H2O from its hydroxy moiety to the position 4 of electrochemically derived o-quinone is occurred. The electrochemical oxidation and reduction of tiron has been successfully accomplished by controlled-voltage coulometry in a redox flow-through type cell and the final electro-reduced product was characterized by spectrophotometric, 1H NMR and mass spectrometric methods. It is demonstrated that the electro-oxidation of tiron follows an ECE mechanism in acidic aqueous solutions, leading to formation of a new compound of para- benzoquinone derivative.