Cu x Fe y V2O5 xerogels were synthesized by doping Cu and Fe into a V2O5 sol via sol–gel process. It retained the desirable layered structure of the V2O5 xerogel. The Cu and Fe doped xerogel cathodes showed high reversibility and their average voltage obtained was about 3.2V versus Li/Li+. Specific capacity of the Cu0.019Fe0.002V2O5 xerogel was more than 150mAh/g at 10mA/g discharge rate in the potential range 2.5–3.9V. After the 30th consecutive cycles, the specific capacity of the Cu0.019Fe0.002V2O5 xerogel electrode maintained 92% of the initial capacity. Impedance analysis revealed that there were two different relaxation processes depending on the equilibrium potentials.