The mineralization of phenol in aerated electrochemical oxidation has been investigated. The results show that a cathodic Fenton process can occur when the Ti-0.3Mo-0.8Ni alloy material is used as cathode in solution containing ferric or ferrous ions; moreover,the reinforcement of cathodic Fenton process on the total organic carbon (TOC) removal rate of phenol is quite distinct. Among the metallic ions investigated, the ferric ion is the best catalyst for the electrochemical mineralization of phenol at initial pH 2.0, and the optimal concentration range is from 50 to 200 mg/L. The favorable pH range and supporting electrolyte (Na2SO4) concentration for mineralization of phenol in solution containing ferrous ions are 1.8-2.3 and below 0.10 mol/L, respectively. UV radiation can improve the TOC removal rate of phenol, but the enhanced effect varies in different solutions. In the solution containing ferric ions, an equal sum or synergetic effect can be observed. The optimal effect of electrolysis system under UV radiation is achieved in the solution containing 50 mg/L Fe3+ with a final removal percentage of 81.3%.