Abstract: The electrochemical oxidation and electrochemiluminescent behavior of homogentisic acid (HGA) has been studied in aqueous solutions over a wide pH range by linear sweep voltammetry, cyclic voltammetry, chronocoulometry at a glassy carbon electrode, by controlled potential electrolysis at a large area spectroscopic graphite electrode, and by spectroelectrochemistry at an optically transparent drilled holes graphite (DHG) electrode in a thin-layer cell. The studies reveal that the electrochemical oxidation of HGA at carbon electrodes is a reversible process involving two-electron, two-proton transfer. In addition to the electrochemical oxidation, the chemical oxidation of HGA by dissolved oxygen was investigated by spectroscopic method combined with voltammetry. It was revealed that HGA is fairly stable in strongly acidic media but readily oxidized by dissolved oxygen in alkaline media giving rise to 1,4-benzoquinone-2-acetic acid, the same product as that of electrooxidation of HGA. This oxidation product is stable in acidic, neutral and weakly alkaline media, but can further degrade in strongly alkaline media yielding oxalate as the final product. The electrochemiluminescent mechanism of HGA in the presence of Ru(bpy)32+ at a glassy carbon electrode was also investigated in detail, based on which a sensitive ECL method for determination of HGA was developed, and the detection limit was 3.0 x 10^-8 mol L-1.