In this work, ferrate(VI) was generated by the electrochemical oxidation of porous magnetite electrodes, made by melting pure magnetite grains. Pretreatment of the anode by cathodic polarization was necessary for ferrate(VI) generation and the achievement of high current efficiency. A electrolyte composition was found to be 16M NaOH. In this electrolyte, the effect of anode current density J on Fe(VI) synthesis rate, current efficiency, and internal cell temperature were studied. An optimum result was obtained at J=3.3mAcm−2, 30°C in 16M NaOH for 5h.