Al2O3 coating is utilized in this work to further improve the cycling stability of LiV3O8 nanoflakes. Surprisingly, three layered Al2O3/LixV2O5/LiV3O8 nanostructure is well formed as confirmed by X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS) results. When used as a cathode for Li-ion battery, the hybrid demonstrates significantly improved cycling stability with a discharge capacity of 203mAhg−1 remaining after 200 cycles at 150mAg−1 and 87.5% of the initial capacity maintaining after 500 cycles at 300mAg−1. Such superior cycling performance should be attributed to the mutual protection of Al2O3 and LixV2O5 layer between Al2O3 and LiV3O8, which can well suppress the damage of LiV3O8 during the long-term cycling process. More importantly, the LixV2O5 middle layer could contribute to the improvement of interfacial electrochemical properties of the hybrid electrode.