A novel method which is based on the hydrothermal reaction was employed to synthesize LiV3O8. First, the mixture solution of LiOH, V2O5, and NH4OH was subjected to the hydrothermal reaction. The hydrothermal treatment yielded a clear, homogeneous solution. The evaporation of this solution led to the formation of a precursor gel. The gel was then heated at different temperatures in the range of 300–600°C. The characterization by X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier transform infrared (FTIR) indicated that LiV3O8 nanorods have been obtained by this novel synthesis method. The electrochemical performance of the LiV3O8 nanorods have been investigated, which indicates that the highest discharge specific capacity of 302mAh/g in the range of 1.8–4.0V was obtained for the sample heated at 300°C, and its capacity remained 278mAh/g after 30 cycles.