LiFePO4/C composite fibers were synthesized by using a combination of electrospinning and sol–gel techniques. Polyacrylonitrile (PAN) was used as an electrospinning media and a carbon source. LiFePO4 precursor materials and PAN were dissolved in N,N-dimethylformamide separately and they were mixed before electrospinning. LiFePO4 precursor/PAN fibers were heat treated, during which LiFePO4 precursor transformed to energy-storage LiFePO4 material and PAN was converted to carbon. The surface morphology and microstructure of the obtained LiFePO4/C composite fibers were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and elemental dispersive spectroscopy (EDS). XRD measurements were also carried out in order to determine the structure of LiFePO4/C composite fibers. Electrochemical performance of LiFePO4/carbon composite fibers was evaluated in coin-type cells. Carbon content and heat treatment conditions (such as stabilization temperature, calcination/carbonization temperature, calcination/carbonization time, etc.) were optimized in terms of electrochemical performance.