Microbial fuel cell (MFC) represents a new method for producing electricity from the oxidation of organic matter. In addition, MFC offers an effective wastewater treatment. The feasibility of using POME wastewater as a substrate was investigated through a two-chambered MFC operated in batch mode for 12 days. The performance of MFC was evaluated under three different anode pH microenvironments of acidic (pH 4), neutral (pH 7) and alkaline (pH 8). Results of experiments indicated that the MFC reactor was able to generate electricity and treat POME wastewater that acted as substrate for MFC. The performance of MFC was found to be dependent on the anode pH microenvironments. Higher power density was observed at neutral condition compared to acidic and alkaline conditions. Furthermore, significant reductions in chemical oxygen demand (COD) in anode chambers were found due to the changes of pH in anode microenvironment. This indicated that effective wastewater treatment of POME in MFC batch experiments. In conclusion, MFC provides an alternative, sustainability and effective method to generate electricity and effectively treat wastewater.