Similar to carbonaceous materials, porous metal oxides have attracted wide attention in energy storage and conversion systems because of their structural advantages, including high activity and electrolyte accessibility. In this work, we report the novel preparation of porous vanadium pentoxide (V2O5) as high performance cathode material for lithium ion batteries. Ketjen black (KB), a porous carbon material, has been employed as hard templates to host precursor species in their porous structures. The porous V2O5 electrode material is prepared after removing the KB carbon framework by calcinating the composites in air. As cathode materials for lithium ion batteries, the porous V2O5 electrodes exhibit high capacity, good cycling stability and rate capability. An initial discharge capacity of 141.1 mA h g−1 is delivered at a current density of 100 mAg−1, very close to the theoretical capacity of 147 mA h g−1.