In this work, we discuss the electrochemical insertion and deinsertion of lithium into poly(3,4-ethylenedioxythiophene) PEDOT–V2O5 nanohybrids by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and powder ex situ X-ray diffraction (XRD) studies with special emphasis on their application potential as cathode materials for rechargeable Lithium batteries. The interlayer spacing of crystalline V2O5 expands from 0.43 to 1.41nm by the intercalation of PEDOT nanoribbons prepared by a microwave irradiation method. Cyclic voltammetry studies of PEDOT–V2O5 hybrid at a slow scan rate of 0.058mVs−1 between 2.0–4.3V vs. Li/Li+, demonstrates that structural transitions of V2O5 are suppressed and more facile intercalation features appear in terms of well-defined reversible cathodic and anodic peaks when compared to that at higher scan rate. Electrochemical Impedance studies of PEDOT–V2O5 hybrid as cathode at ambient temperature with lithium metal foil as both counter and reference electrodes in 1M LiPF6 in a mixture of ethylene and diethylcarbonate (50:50 by volume) between the range 2.0–4.3V reveals the usefulness of these materials. The observed capacity fading during cycling in terms of surface passivation and structural transformations is also investigated by CV, EIS and XRD analysis.