Some electrochemical kinetic parameters of Ce^4^+/Ce^3^+ system have been obtained by means of RDE and RRDE techniques, which demonstrated the feasibility of assembling a completely new Ce^4^+/Ce^3^+- V^2^+/V^3^+ redox flow cell. One layer of oxidation film forms at the surface of both Pt and GC electrodes in such system, which inhibits the oxidation of Ce^3^+ on both electrodes while enforces the reduction of Ce^4^+ on the Pt. There is also a competition between the oxidation of Ce^3^+ and the evolution of O2, therefore the anodic current density should be strictly controlled in the range of 2～8 mA. cm^-^2 for obtaining higher oxidation efficiency of Ce^3^+.

Key words: CERIUM, VANADIUM, OXIDATION REDUCTION REACTION, OXIDE FILM