Nowadays, electrochemical advanced oxidation processes, Fenton process, have attracted a lot of attention as compared to conventional degradation. Regarding the Fenton catalyst, iron oxide has been known as an efficient catalyst and demonstrated in degradation of organic pollutant. The metal doping into iron oxides has been shown to enhance the degradation rate due to rich redox reaction. However, there is only few studies on the anion doping. It is known that anion doping is able to enhance the electrical conductivity of the oxide. In this study, novel cation and anion co-doped iron oxide has been firstly demonstrated for electron-Fenton catalyst. The synergistic effect of cation and anion doping is favorable to improve the selectivity of hydrogen peroxide, which thus can be utilized for electro-Fenton degradation of organic pollutant. The electro-Fenton degradation performance has been evaluated through degradation of tetracycline at different condition. At the optimized condition, the obtained material generates hydrogen peroxide >150 mgL^-1 and tetracycline degradation efficiency of 100% within 2-h. This novel oxide catalyst can be regarded as a promising catalyst for wastewater treatment.