We have studied the electrochemical behavior of Tb0.11V2O5 electrodes in propylene carbonate and LiClO4. The techniques used in the study were cyclic voltammetry, discharge/charge polarization, FTIR and XRD. The Tb0.11V2O5 compound was prepared using the xerogel route and the composite electrodes were membranes prepared with PVDF-binder and carbon. The results show that the Tb doping improves the electrochemical performance of V2O5 due to the bonding of the earth-rare ions and the residual H2O in the V2O5 structure. The capacity fading was reduced, the specific reversible capacity was 330mAg−1 (C/4, cut-off 3.7–2.0V) and the voltage presented a large plateau at 2.5V for the Tb0.11V2O5 electrodes. The charge transfer between Li and Tb0.11V2O5 does not involve the oxidation–reduction of the Tb3+ ions.