The electrochemical oxidation of cerium(III) was carried out using divided and undivided electrochemical cells in nitric acid medium. It was found that divided cell with Nafion 324 as the separator gave good conversion yield with high current efficiency compared to the undivided cell. The efficiency of the divided electrochemical cell was further optimized in terms of cell voltage, temperature, flow rate of solution recirculation, concentrations of Ce(III) and nitric acid. The better conditions for 1 M Ce(III) in 3 M nitric acid were found to be 2.5 V, 363 K and 100 mL/min recirculation flow rate based on the current efficiency under the experimental conditions investigated. The Ce(IV) oxidant produced was used as a mediator for the mineralization of phenol. The mineralization efficiency of the cerium mediated electrochemical oxidation was found rapid and higher compared to the direct electrochemical oxidation based on CO2 evolution under the same conditions.