Electrochemical and peroxidase-catalyzed oxidation of epinephrine (EPI) has been studied. In the electrochemical studies a single well-defined, 4e, 4H(+), pH-dependent oxidation peak was observed in square wave and cyclic sweep voltammetry at edge plane pyrolytic graphite electrode. In the reverse sweep a redox couple was observed. The decay of the UV-absorbing intermediate generated and the first-order rate constants were calculated at different pH and were found to be similar to 6.3 x 10(-3) s(-1). The detection limit and sensitivity are found to be 17 x 10(-8) M and 2.325 mu A mu M-1 respectively. At pH 7.2, the electro-oxidation product was characterized using NMR and DEPT studies as leucoadrenochrome. The peroxidase-catalyzed oxidation was carried out using horseradish peroxidase and initiated by adding H2O2. The identical spectral changes, rate constants and product formed during electrochemical and enzymatic oxidation suggest that the same intermediate species is generated during both the oxidations. A tentative pathway for the oxidation of EPI has been suggested. It is concluded that the electrochemical and peroxidase-catalyzed oxidation of EPI proceed by an identical pathway. (C) 2011 Elsevier Ltd. All rights reserved.