[en] Conditions for electrochemical generation of cerium(IV) at glassy carbon in acetic acid in the presence of alkali-metal acetates and sodium perchlorate, respectively, were investigated. A high current efficiency was achieved in anodic oxidation of cerium(III) in acetate supporting electrolytes. Coulometric titration methods for the determination of reducing substances with the generated oxidant were also developed. The end-points were determined by the biamperometric and bipotentiometric methods. The error of the determinations was less than ± 2%