Surface modified-LiV3O8 cathode materials with Al2O3 are successfully synthesized via a facile thermolysis process. The 0.5 wt.% Al2O3-coated LiV3O8 exhibits an enhanced cyclic stability at various charge-discharge current densities. At a current density of 100 mA ga1, it delivers an initial specific discharge capacity of 283.1 mAh ga1 between 2.0 and 4.0 V. Moreover, high capacities of 139.4 and 118.5 mAh ga1 are obtained at the 100th cycle at current densities of 2000 and 3000 mA ga1, respectively. The improved electrochemical performance is attributed to the Al2O3 coating, which can hinder the irreversible phase transformation and act as a protective layer to prevent the active material from direct contact with electrolyte. Furthermore, the formation of a LiaVaAlaO solid solution at the LiV3O8/Al2O3 interface provides a fast Li+ diffusion path which is of benefit to the electrochemical behaviors.