The Li–V–O composite (n Li:n V =1:3.5) was synthesized by a hydrothermal method and post-treated at 300°C. XRD analysis confirms that the composite is a binary LiV3O8–V2O5 composite system with the formula of 0.8LiV3O8·0.2V2O5. The composite consists of small laminar nanocrystallites with numerous cavities between the stacked laminar nanocrystallites, which can provide good channels for Li+ transfer during charge–discharge cycling. The initial discharge capacities of LiV3O8 and 0.8LiV3O8·0.2V2O5 samples were 276 and 365mAh/g after 20 cycles, the discharge capacities of the two samples were 197.6 and 304mAh/g, respectively. Smaller capacity loss indicates that the capacity retention of the composite is superior to that of bare LiV3O8 cathode.