The electrochemistry of the nanostructured electrodes produced and their use as the anode material in Li-ion batteries was reported. Poly(3,4-ethylenedioxythiophene) (PEDOT) was utilized as the conducting polymer because of the excellent electrochemical activity and electronic conductivity attainable with this material. A thin PEDOT film of 100 nm thickness across the entire film was deposited onto aligned carbon nanotube (ACNT) arrays by CVP using ferric p-toluenesulfonate (Fe(III) tosylate) as oxidant. The SEM image of this ACNT/PEDOT composite film indicates that the PEDOT deposited by VPP formed a continuous film on the top of the ACNT array. It was found that the PEDOT film was not sufficiently mechanically robust to support the ACNT array. The aligned carbon nanotube layer was found to be adherent and was not removed by rubbing or abrasion on a hard surface.