Abtract LiNi0.80Co0.15Al0.05O2 has been widely pursued as an alternative to LiCoO2 cathode materials for lithium ion batteries because of its high capacity and acceptable cycling property. However, that NCA can react with commercialized electrolyte during cycling restrains its wide use. Here, olivine structured LiMnPO4 has been introduced to modify the surface of NCA by a sol-gel method. Characterizations from structure, morphology and composition analysis technologies demonstrate that a LiMnPO4 layer has been uniformly coated on NCA particles. The electrochemical performance and thermo stability of modified samples are characterized by electrochemical tests, XRD and metallic nail penetration tests. The olivine structured skin, which provides structural and thermal stability, is used to encapsulate the high powered core via using the effective coating technique. The modified material displays a high discharge capacity of 211.0mAhg−1 at 0.2C and better rate performance and promoted cycling stability than the uncoated control sample. Furthermore, the thermal stability of coated sample in the delithiated state is upgraded to the pristine powders remarkably.