Lithium vanadate, LiVO3, has been successfully synthesized by a soft chemistry route with subsequent calcinations. The influence of synthesis temperature on the structure properties including lattice parameters and crystallite size were investigated by X-ray powder diffraction. The LiVO3 compound fabricated at 350 °C has the smallest particles with diameters ranging from 500 nm to 1 μm, and possesses the best performance including high discharge capacity, good rate capability and cyclic stability as cathode materials for lithium ion batteries. Highly stable specific capacities of 257, 233, 203.8, 173.7 and 141.9 mA h g−1 can be achieved at current densities of 100, 200, 400, 800 and 1500 mA g−1, respectively. The phase transition of the discharged electrode has been evaluated by the ex-situ XRD techniques. Electrochemical impedance spectra (EIS) measurements were carried out to determine the influence of phase transition on the lithium diffusion coefficients.