Bio-electrochemical treatment (BET) documented effective degradation of real field petroleum sludge over the conventional anaerobic treatment (AnT). BET (41.08%) operation showed enhanced total petroleum hydrocarbons (TPH) removal over AnT (20.72%). Aromatic fraction visualized higher removal (75.54%) compared to other TPH fractions viz., aliphatics, asphaltenes and NSO (nitrogen, sulfur and oxygen) during BET operation. Higher ring aromatics (5-6) documented easy degradation in BET, while AnT was limited to lower ring (2-3) compounds. Voltammetric analysis evidenced simultaneous redox behavior during BET operation due to presence of graphite electrode as electron acceptor, while AnT showed extended reduction behavior only. Self-induced primary and secondary oxidation reactions and capacitive-deionization might have enhanced the degradation capability of BET. BET documented higher charge/capacitance (2810 mJ/1120 mF) than AnT (450 mJ/180 mF). Power output corroborated well with observed results supporting BET performance as fuel cell. Electrodes offer a potential alternative electron acceptor for promoting the degradation of organic contaminants. (C) 2011 Elsevier Ltd. All rights reserved.