A new simple synthetic method was employed to produce LiV3O8 compound in which LiOH, V2O5 and NH4OH were used as the starting reactants. At first, V2O5 reacted with LiOH and NH4OH in liquid solutions to obtain a compound containing Li and V, which was then calcined at 370, 450 and 550°C for 8 h, respectively. The electrochemical properties of the LiV3O8 compound were studied by galvanostatic charge–discharge, and the highest capacity of 274 mAh g−1 was obtained for the LiV3O8 compound calcined at 370°C in the range of 1.8–4.0 V. In the fifteenth cycle, its capacity remained 257 mAh g−1. The inspections by X-ray diffraction and SEM indicated that different calcining temperatures resulted in different structure, which resulted in different discharge capacity.