Electrochemical degradation of phenol was studied in an undivided cell with a Ti/IrO2/RuO2 anode and a carbon/polytetrafluoroethylene (C/PTFE) O2-fed cathode which produced hydrogen peroxide (H2O2) by the electro-reduction of dissolved oxygen. The effect of current density, supporting electrolyte concentration and initial pH on the removal efficiency of phenol were investigated systematically. Results indicated that the optimal removal efficiency of phenol was achieved under the conditions of current density of 39 mA/cm2 and supporting electrolyte concentration of 0.02 mol/L. The phenol removal efficiency in the neutral condition was higher than that of acidic and basic conditions. The chemical oxygen demand (COD) and total organic carbon (TOC) removal achieved 71.6% and 63.6% for 100 min’s electrolysis, respectively. Benzoquinone, maleic acid, oxalic acid, acetic acid and formic acid were identified as intermediates by HPLC. A general phenol degradation pathway involving all these intermediates was proposed.