The addition of nano Fe3O4 is beneficial to boost the transient charge storage of the anode accompanying with the enhancement of power performance in microbial fuel cells (MFCs) in our previous study. Here we found that both the anodic open circuit potential and the current increased when comparing the AcFeM (Fe3O4 added activated carbon anode) with the AcM (activated carbon anode), indicating that the Fe3O4 dynamically accelerated the anodic electron transfer although it thermodynamically limited the anode potential. The net storage capacity initially increased followed by a decrease with the maximum capacitance of 574.6 C m(-2) (AcFeM) and 459 C m(-2) (AcM) under 20 min of open circuit interval. The Fe3O4/Fe(II) possibly stored charges temporarily as a solid-state electron shuttle. (C) 2013 Elsevier Ltd. All rights reserved.