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 159mAhg−1 at 0.1C and 120mAhg−1 at 10C.