A LiFePO4/C submicrofibers composite was prepared by a facile electrospinning method using LiNO3, Fe(NO3)3·9H2O, NH4H2PO4, citric acid and poly(4-vinyl)pyridine (PVP) as raw materials, and its physical properties and electrochemical performance were investigated by X-ray diffraction (XRD) spectroscopy, scanning electron microscopy (SEM), transmission electron microscope (TEM), energy dispersive analysis of X-ray (EDAX), N2 adsorption/desorption measurement and electrochemical tests. The crystal size of LiFePO4 fibers is about 30nm calculated by Debye-Scherrer equation and the LiFePO4 nanofibers aggregate to LiFePO4/C submicrofibers composite with diameters of about 270–372nm. The LiFePO4 submicrofibers are covered by an amorphous carbon layer with a thickness of about 2.6nm and the LiFePO4/C submicrofibers composite with mesopores exhibits amazing high surface area of 167.729m2 g−1. The LiFePO4/C submicrofibers composite displays high initial discharge capacities of 166 and 168mAhg−1 and excellent cycle performance at 0.1C (17mAhg−1) in the voltage range of 2.5–4.5V at 25 and 55°C, respectively. Even at high rate of 5C, the LiFePO4/C submicrofibers composite delivers discharge capacities of 132 and 138mAhg−1 and excellent cycle performance at 25 and 55°C, respectively. The results indicate that the electrospinning method is promising to prepare LiFePO4/C composite with high electrochemical performance.