As the acceleration of urbanization, the organic pollutants in wastewater have been more complex and persistent. However, these toxic materials could not be effectively removed by conventional wastewater treatment, posing a serious threat to the eco-environment and human health. Microbial fuel cell (MFC), an emerging renewable technology, can directly convert the chemical energy from organic compounds into electricity by microbial catalysis. Electrode design is one of the most important factors in affecting the pollutants degradation and power output capacity. Hence, this review demonstrates the latest developments of organic pollutants removal along with electricity generation by the anode/cathode modification in MFC. Furthermore, the applications of MFC electrode materials in wastewater treatment field are prospected.