Lithium trivanadate (LiV3O8) compound was prepared under different conditions and characterized by the Rietveld-refined X-ray diffraction, scanning electron microscopy (SEM), and Brunauer−Emmett−Teller (BET) surface area and density techniques. The electrochemical performances of the LiV3O8 compounds prepared under different conditions were compared. LiV3O8 rods prepared by the surfactant-assisted polymer precursor method were found to perform well, delivering a discharge capacity of 230 (±5) mA·h/g at the end of the second cycle, with an excellent capacity retention of 99.52% at the end of the 20th cycle, for a current density of 30 mA/g. LiV3O8 rods delivered a discharge capacity of 135 (±5) mA·h/g at the end of 350 cycles, for a current density of 240 mA/g, and reasonably high capacity values were achieved at the different current rates. Impedance spectroscopic studies during the first and eighth cycles at various voltages are analyzed and discussed.