The iron-fed fuel cell is an effective technology to recover iron and electricity from acid mine drainage (AMD). However, this technology suffers from the problem of performance degradation which significantly reduces its power output during long-term operation. In this work, the performance degradation of iron-fed fuel cell is comprehensively evaluated with the objective to elucidate the mechanisms involved in such a phenomenon. The iron contamination is identified as the main cause responsible for the performance degradation of fuel cell. The iron contaminant is present in the form of alpha-FeO(OH), which is the main product recovered by the iron-fed fuel cell. Both the electrode and membrane are deteriorated by iron contamination, whereas the membrane deterioration is more significant. Fed-batch experiments demonstrate the performance loss of fuel cell due to contamination of membrane is more than 50% greater than the performance loss due to contamination of electrode. The alpha-FeO(OH) contaminant not only forms fouling layers on the surfaces of carbon electrode and membrane, but also migrates into the membrane to damage the membrane structure. As a result, both the charge transfer and mass transfer resistances of fuel cell are dramatically increased, which leads to delayed electro-oxidation kinetics of Fe(II). (C) 2013 Elsevier B.V. All rights reserved.