A system of capillary electrophoresis with electrochemiluminescence detection (CE-ECL) together with UV spectroscopic and electrochemical methods were used to study the chemical oxidation of p-hydroxyphenylpyruvic acid (pHPP) by dissolved oxygen in aqueous solution. The pHPP was observed to be readily oxidized by dissolved oxygen in alkaline solution and yielded a compound that strongly enhanced the electrochemiluminescence of Ru(bpy)23+. This compound was separated and detected by a new CE-ECL system and revealed to be oxalate by being compared with an authentic sample of oxalate. The chemical oxidation mechanism of pHPP by dissolved oxygen was discussed in this paper.