V2O5 xerogel films modified by poly(ethylene-oxide) (PEO) were obtained via sol-gel method. Investigations were conducted by X-ray diffractometry (XRD), Fourier transformation infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry. The results show that when V2O5 xerogel is modified by the intercalation of PEO, the H atoms in PEO are hydrogen-bonded with the O atoms in the V=O bonds of V2O5 xerogel, which effectively shields the electrostatic interaction between V2O5 interlayer and Li+ions. The reversibility of insertion/extraction of Li+ions is greatly improved with the modification of PEO in V2O5 xerogel.