Lithium vanadium tetroxide (Li3VO4) anode material has been synthesized by a fast sol–gel method based on spontaneous chemical reactions. The crystal structures, surface morphologies and electrochemical performances of the Li3VO4 samples calcined at different temperatures are investigated. In the potential range of 0.02–3.0V, the sample sintered at 600°C shows the highest initial charge capacities of 276.2mAhg−1, 258.4mAhg−1, 201.4mAhg−1, at 0.1C, 0.2C and 0.5C, respectively. After 50 cycles, the charge capacities still retains 310.5mAhg−1, 278.1mAhg−1 and 222.4mAhg−1 at 0.1C, 0.2C and 0.5C, respectively. It shows fast sol-gel method is promising in synthesize stable Li3VO4 for EV or HEV applications.