A novel electrocatalysis method for phenol degradation was described using a beta-PbO2 anode modified with fluorine resin and a Ni-Cr-Ti alloy cathode. In case of air sparging at the cathodic zone, the techniques of anodic-cathodic electrocatalysis (ACEC) and ferrous ion catalyzed anodic-cathodic electrocatalysis (FACEC) in the presence of iron(II) were developed. Both of ACEC and FACEC were more effective than anodic electrocatalysis (AEC). The percentage of phenol eliminated by FACEC could increase by nearly 30% compared with that of AEC, and the current efficiency could reach to 70%. Important operating factors such as ferrous ion concentration, air-sparging rate and applied current were investigated and it was found that such beneficial effects could be achieved at a suitable current and ratio of the concentration of ferrous ion to the air sparged. The mechanism of phenol degradation is proposed to be the generation of hydroxyl radicals concerned with the two electrodes. Results also indicated that the process provided an efficient way to regenerate ferrous ion compared with the conventional Fenton's system.