The performance of carbon rod (CR), titanium sheet (TS), stainless steel woven mesh (SSM) and copper sheet (CS) cathode materials are investigated in microbial fuel cells (MFCs) for simultaneous electricity generation and Cu(II) reduction, in multiple batch cycle operations. After 12 cycles, the MFC with CR exhibits 55% reduction in the maximum power density and 76% increase in Cu(II) removal. In contrast, the TS and SSM cathodes at cycle 12 show maximum power densities of 1.7 (TS) and 3.4 (SSM) times, and Cu(II) removal of 1.2 (TS) and 1.3 (SSM) times higher than those observed during the first cycle. Diffusional resistance in the TS and SSM cathodes is found to appreciably decrease over time due to the copper deposition. In contrast to CR, TS and SSM, the cathode made with CS is heavily corroded in the first cycle, exhibiting significant reduction in both the maximum power density and Cu(II) removal at cycle 2, after which the performance stabilizes. These results demonstrate that the initial deposition of copper on the cathodes of MFCs is crucial for efficient and continuous Cu(II) reduction and electricity generation over prolonged time. This effect is closely associated with the nature of the cathode material. Among the materials examined, the SSM is the most effective and inexpensive cathode for practical use in MFCs. (C) 2016 Elsevier B.V. All rights reserved.