LiCo1/3Mn1/3Ni1/3O2 hollow spheres with an average outer diameter of 300nm and a wall thickness of about 50nm are prepared by using carbon spheres as template. They demonstrate excellent electrochemical performance, including high discharge capacity and rate capability. At a current rate of 0.2C (34mAg−1, 0.34mAcm−2), cathode materials constituted by the hollow spheres display a discharge capacity of 175.4mAhg−1. Even at a current rate of 10C (1700mAg−1, 17mAcm−2), the discharge capacity also keeps at 91.5mAhg−1. The reasons lie in that the hollow structure has a large surface to contact with liquid electrolyte, resulting in a better electrochemical performance at high charge/discharge rate.