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The two-chamber microbial fuel cells (MFCs) were constructed with excess sludge as the anodic substrate and CuSO4 solution as the catholyte. The start up method, degradation of the anodic sludge, removal of the Cu2+ and products on cathode were investigated in the study. The results of batch experiments showed that Cu2+ can be used as cathodic electron acceptors, e. g. a stable voltage output of 0.478 V and a maximum power density of 536 mW/m3 were obtained at external resistance of 1 000 omega and Cu2+ concentration of 6 400 mg/L. The Cu2+ contained in wastewater could be removed effectively by the MFC process, e. g. 97.8% of Cu2+ was removed in a MFC reactor at the end of 288 h with initial Cu2+ concentration of 1 000 mg/L and external resistance of 0 omega. The cathodic products depended on cathodic reducibility, most of Cu2+ was deposited as Cu2O and a small part as Cu4 (OH), 6SO4 with lower cathodic reducibility, metal copper deposited on the cathode with higher cathodic reducibility. Using excess sludge as anodic substrate could support the MFCs for long-term operation. The acclimation stage of the exoelectrogenic bacteria on the anode had an impact on MFC performance and cathodic reduction of Cu2+, and the stability of exoelectrogenic biofilm on anode could be determined by monitoring the anode potential. The MFC with excess sludge as anodic substrate can degrade organic matter in sludge and accomplish Cu(2+) -containing wastewater treatment and copper recovery simultaneously.