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A series of hybrid electrode materials, poly(3,4-ethylenedioxythiophene)/V2O5, has been synthesized using an oxidative insertion and polymerization reaction. FTIR, X-ray diffraction and transmission electron microscopy studies have shown that the incorporation of polymer between V2O5 slabs leads to an enhanced bidimensionality. The electrochemical lithium capacity has been increased up to ∼330 mAh/g at the second discharge in the range of 2.0–4.4 V vs. Li. This improvement of electrochemical performance compared to pristine V2O5 is attributed to the higher electric conductivity and enhanced bidimensionality. [Copyright &y& Elsevier]