Vanadium oxide (V2O5/V2O5 hydrates) sol–gel coatings on lithium cobalt oxide (LiCoO2) are investigated as a means are prepared to improve the cycleability at a high-charge cut-off voltage. The V2O5 sol was prepared by a melt-quenching method. The crystal structure and morphology of the samples are examined by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The charge and discharge characteristics, including cycleability, are measured at room temperature, and the electrochemical properties of bare and coated LiCoO2 are compared. Overall, a vanadium oxide coating on LiCoO2 improves the cycleability at a high-charge cut-off voltage.