Poly(3,4-ethylenedioxythiophene) (PEDOT) and multi-walled carbon nanotubes (MWCNTs) were employed to modify commercial V2O5 to prepare composite electrode materials for lithium-ion batteries. It was found that MWCNTs improved the electric conductivity of the MWCNT-modified V2O5. In comparison, PEDOT not only improved the electric conductivity of the PEDOT-modified V2O5 but also enhanced its stability against electrolyte. When applied as a cathode for lithium ion batteries, the sample modified with PEDOT performed the best, followed by the sample modified with both MWCNTs and PEDOT, and the sample modified with MWCNTs only.