A pomegranate-structured FePO4/C composite was synthesized via a combination of electrospinning and high temperature reaction using micron-level FePO4 and polyacrylonitrile (PAN). Systematic studies on synthesis, modification, and characterization of FePO4/C composites were conducted. The FePO4/C composites delivered a specific discharge capacity of 109 mAh g(-1) at 0.2 C and 39 mAh g(-1) at 10 C, which were comparable with the reported nanometer-level FePO4. We demonstrated that the three-dimensional net-like structure covered by porous carbon layers could highly enhance the electrochemical performance of FePO4. Crown Copyright (C) 2012 Published by Elsevier Ltd. All rights reserved.