Carbon-coated Li3VO4 sample is synthesized by a simple sol–gel method. X-ray diffraction and X-ray photoelectron spectroscopy results show that single-phase Li3VO4 can be obtained in a reducing atmosphere with the valence of vanadium of +5. The final product sintered at 650 °C demonstrates a favorable electronic conductivity with 6.12% residual carbon. Electrochemical testing shows that the carbon-coated Li3VO4 sample display a discharge capacity of 662.6 mAh g−1 and 507.4 mAh g−1 at 0.18C in the first and the second cycle, respectively, and a reversible capacity (charge capacity) of ∼480.0 mAh g−1 can be obtained in the second cycle. Furthermore, the discharge–charge capacity of the sample can retain ∼180 mAh g−1 and ∼90 mAh g−1 at 12C and 40C, respectively.