The anodic discharge of water to produce adsorbed hydroxyl free radicals(*OH) is considered to be a prerequisite to anodic O-transfer reactions at a PbO2 electrode. In this work, a method was studied by means of high-performance liquid chromatography(HPLC) combined with electrochemical detection(ED) so as to investigate the production of hydroxyl free radicals(*OH) in the process of the anodic discharge of H2O at a PbO2 electrode. The voltammetric data obtained at the PbO2 electrode for the oxidation of salicylic acid to salicylate hydroxylation products(DHBAs) and the detection of DHBAs by means of HPLC-ED confirm the proposed mechanism.