LiVPO4F/C composites with better electrochemical performance were prepared by calcination of LiF and amorphous vanadium phosphorus oxide (VPO) intermediate synthesized by a sol–gel method using H3PO4, V2O5 and citric acid as raw materials. The properties of LiVPO4F/C composites were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical tests. The analysis of XRD patterns and Fourier transform infrared spectra (FTIR) reveal that VPO intermediate prepared by sol–gel method is amorphous and VPO4 may exist in VPO intermediate. The compositions of LiVPO4F/C composites are related to the calcination temperature for preparation of amorphous VPO/C intermediate and LiVPO4F/C composite prepared by VPO/C synthesized at 700°C consists of a single crystal phase of LiVPO4F. The electrochemical tests show that LiVPO4F/C composite prepared by VPO/C synthesized at 700°C exhibits higher discharge capacity and excellent cycle performance. This LiVPO4F/C composite displays discharge capacity of 133 mAh g−1 at 0.5 C (78 mA g−1) and remains capacity retention of 96.8% after 30 cycles, even at a high rate of 5 C, the composite exhibits high discharge capacity of 115 mAh g−1 and capacity retention of 97% after 100 cycles.