The biodegradation of total organic carbon (TOC) and polychlorinated biphenyls (PCBs) in sediment was studied in different treatments. This study showed that the combined application of a sediment microbial fuel cell (SMFC) and surfactant led to the highest removal efficiencies (58.91% of TOC and 43.26% of PCBs) after 60 days of operation, and produced the maximum power output (0.821 V of voltage and 18.30 W m À3 of power density). TOC and PCBs can diffuse between sediment and overlying water. The overlying water of natural anaerobic degradation sediment led to the greatest increase in PCB concentration (4.43 ng L À1 ), following the addition of 6 mg kg À1 PCBs into sediments. Considering the enhanced degradation and high power output, the combined application of the SMFC and surfactant addition offered a more efficient and promising way to purify the contaminated sediment and overlying water.