A nano-crystalline MgO coating was formed on the surface of LiCoO 2 particle via a sol-gel method. MgO coating can improve the cycling stability of LiCoO 2 significantly. After the 40th cycle a discharge capacity of more than 120mAh/g was remained for 1mol% MgO-coated LiCoO 2 , while only 13mAh/g for pristine LiCoO 2 when both charged up to 4.7V. During heat treatment and charge/discharge process, Mg 2 + in coatings will diffuse into LiO 2 -layers of LiCoO 2 , which does not cause any detectable shift in X-ray diffractometer (XRD) peak positions, but does impact the XRD peak intensity due to the aberrance of (003) plane. Mg 2 + ions existing in LiO 2 -layers will stabilize the lattice structure of LiCoO 2 , hence improve the cycling performance of LiCoO 2 cathode. More MgO coating on LiCoO 2 is detrimental to the electrochemical properties of LiCoO 2 cathode, probably due to the electrochemical inactivity of MgO particles.