A novel kind of microsized nest-like LiFePO4/C architectures was synthesized by solvothermal method using inexpensive and stable Fe3+ salt as iron source and ethylene glycol as mediate. A layer of carbon could be coated directly on the surface of LiFePO4 crystals and the nest-like unique structures offer the cathode materials with high reversible capacity, excellent cycling stability and high rate performance. The reversible capacity can maintain 159 mAh g(-1) at 0.1C and 120 mAh g(-1) at 10 C. Crown Copyright (C) 2012 Published by Elsevier Ltd. All rights reserved.