LiVO3 materials are synthesized by combustion method with oxalic acid as fuel. Owing to its relatively low crystallization and small particle size, the LiVO3 calcined at 450 °C for 2 h displays optimal electrochemical performances, delivering a high discharge capacity of 298.4 mAh g−1 and 262.5 mAh g−1 between 1.0 and 3.5 V at a current density of 50 mA g−1 and 500 mA g−1 respectively, and exhibiting good cyclic stability. In this work, the chemical diffusion coefficient of Li+ (D Li+) in the LiVO3 electrode is determined by electrochemical impedance spectroscopy (EIS) and galvanostatic intermittent titration technique (GITT). The value calculated by EIS is in the range of 10−9–10−8 cm2 s−1, while it calculated by GITT is 10−9.5–10−8 cm2 s−1.