Vanadium Oxide (V2O5) nanobelts were synthesized, intercalating with a conducting polymer polyethylene glycol (PEG), by simple hydrothermal process. Investigations were conducted by X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR), Differential scanning calorimetry (DSC) and Scanning electron microscopy (SEM) and Cyclic voltammetry (CV). The results show that the H atoms in PEG are hydrogen bonded with the O atoms of the VO bonds of the V2O5, which effectively shielded against electrostatic interaction between the V2O5 interlayer and Li+ ions when the V2O5 is modified by the intercalation of PEG. The broad endothermic peak temperature increases with increasing concentration of PEG content in V2O5 nanobelts. Cathodic performance of PEGxV2O5 (x =0, 0.5 and 1) nanobelts for Li ion rechargeable battery was investigated. The V2O5 nanobelts exhibit a high specific discharge capacity of 397.61mAhg−1 for Li ion electrochemical intercalation.