LiY0.1V3O8 compound was successfully prepared by using a simple, rapid and easily scaled up method, i.e. the rheological phase reaction method. The microstructural characteristics of LiY0.1V3O8 materials were examined by X-ray diffraction and scanning electron microscopy (SEM). Compared with LiV3O8 compound, the LiY0.1V3O8 shows expanded crystal lattices, and the expansion is more significant along the c-axis. The electrochemical properties of the as-synthesized LiY0.1V3O8 compounds were investigated. It was found that the LiY0.1V3O8 electrodes exhibited better reversibility and higher capacities than LiV3O8 electrodes. The reasons for the improved electrochemical performance of the LiY0.1V3O8 electrodes are also discussed.