A cathode material, LiV3O8, for rechargeable lithium-based batteries has been prepared via a combined freeze-drying method and appropriately post-treated in argon atmosphere. It was found that the sample post-treated at 300°C in Ar has the optimal performance. Electrochemical tests performed on this material demonstrated its very high insertion capacity of 347mAhg−1 (3.7 Li+ per LiV3O8) at a current density of 50mAg−1 (C/6). Most important is that it displayed an excellent cycling stability and after 60 cycles, a discharge capacity with 351mAhg−1 was obtained. It was proposed that a short-range crystallographic order had a stronger influence on the electrochemical performance of an electrode material in this work, instead of the surface area, particle size and crystalline degree, etc.