LiVO3 is synthesized via a ball-milling route followed by a solid-state reaction at different temperatures. As cathode materials for lithium ion batteries, the electrochemical performances of LiVO3 are investigated by galvanostatic charge–discharge test and electrochemical impedance spectroscopy (EIS). The LiVO3 compound synthesized at 350 °C possesses the optimal performance, delivering an initial discharge capacity of 302.5 mAh g−1 between 1.0 V and 3.5 V at a current density of 50 mA g−1, and exhibiting a good cycling stability. Li-ion diffusion coefficient of 10−9.5–10−8 cm2 s−1 in the LiVO3 electrode is calculated by galvanostatic intermittent titration technique (GITT). The good performances can be attributed to its relatively low crystallization and small particle size.