Discharging LixV2O5 electrodes beyond x = 1 leads to an irreversible transformation of the delta-phase into a gamma-phase. The achievement of this transformation is governed by the number of cycles, the depth of discharge as well as by grain size and morphology of the active material. The study of the OCV versus time curves, at various stages of discharge, reveals a rather complex behavior resulting from diffusional and phase transition phenomena.