Based on energetic analysis, a novel approach for copper electrodeposition via cathodic reduction in microbial fuel cells (MFCs) was proposed for the removal of copper and recovery of copper solids as metal copper and/or Cu(2)O in a cathode with simultaneous electricity generation with organic matter. This was examined by using dual-chamber MFCs (chamber volume, 1 L) with different concentrations of CuSO(4) solution (50.3 +/- 5.8, 183.3 +/- 0.4, 482.4 +/- 9.6, 1007.9 +/- 52.0 and 6412.5 +/- 26.7 mg Cu(2+)/L) as catholyte at pH 4.7, and different resistors (0, 15, 390 and 1000 Omega) as external load. With glucose as a substrate and anaerobic sludge as an inoculum, the maximum power density generated was 339 mW/m(3) at an initial 6412.5 +/- 26.7 mg Cu(2+)/L concentration. High Cu(2+) removal efficiency (> 99%) and final Cu(2+) concentration below the USA EPA maximum contaminant level (MCL) for drinking water (1.3 mg/L) was observed at an initial 196.2 +/- 0.4 mg Cu(2+)/L concentration with an external resistor of 15 Omega, or without an external resistor. X-ray diffraction analysis confirmed that Cu(2+) was reduced to cuprous oxide (Cu(2)O) and metal copper (Cu) on the cathodes. Non-reduced brochantite precipitates were observed as major copper precipitates in the MFC with a high initial Cu(2+) concentration (0.1 M) but not in the others. The sustainability of high Cu(2+) removal (> 96%) by MFC was further examined by fed-batch mode for eight cycles. (C) 2011 Elsevier B.V. All rights reserved.