The electrochemical oxidation of 3,5-di-tert-buthylcatechol in the presence of homocysteine was used for the selective electrochemical determination of homocysteine in the presence of cysteine and glutathione at a glassy carbon and a glassy carbon electrode modified with carbon nanotube. The results revealed that the electrochemically generated 3,5-di-tert-butylcyclohexa-3,5-diene-1,2-dione exhibits high catalytic activity toward homocysteine oxidation at reduced over-potential and low catalytic activity for oxidation of cysteine. The catalytic activity 3,5-di-tert-butylcyclohexa-3,5-diene-1,2-dione toward cysteine was suppressed in the presence of 4-N,N-dimethylaminocinnamaldehyde. Contrary to homocysteine and cysteine, the reaction of glutathione with 3,5-di-tert-butylcyclohexa-3,5-diene-1,2-dione is a substituation reaction. This method exhibits three dynamic linear ranges of 2.5 to 10 mu mol L-1, 10 to 100 mu mol L-1 and 100 to 1000 mu mol L-1, and a lower detection limit (3 sigma) of 0.89 +/- 3.53% mu mol L-1 for homocysteine. (C) 2014 Elsevier Ltd. All rights reserved.