LiFePO4/C composite nanofibers were synthesized by calcination of the [LiOH + Fe(NO3)(3) + H3PO4]/PVP electrospun nanofibers. Polyvinyl pyrrolidone (PVP) was used as the electrospinning template and carbon source. During the calcination [LiOH + Fe(NO3)(3) + H3PO4] were transformed to LiFePO4 and PVP was decomposed into carbon. The morphology and properties of the as-prepared samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Brunauer-Emmett-Teller (BET) specific surface area analysis, electrochemical impedance spectroscopy and galvanostatic charge-discharge measurements. The results indicate that the mean diameter of as-prepared LiFePO4/C composite nanofibers is 179.08 +/- A 29.66 nm and the BET specific surface area is 66.59 m(2) g(-1). The addition of carbon does not affect the structure of LiFePO4, but improves its electrochemical performances. At the current density of 0.2 C, the initial discharge capacity of LiFePO4/C electrode is 133.6 mAh g(-1) and there is no obvious capacity fading after 100 cycles. The formation mechanism of the LiFePO4/C composite nanofibers was also proposed.