CaF 2 -coated LiMn 1/3 Ni 1/3 Co 1/3 O 2 cathode material is prepared via a wet chemical process followed by a solid state reaction. High-resolution transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) show that the well coated CaF 2 layer has a thickness of 4–8nm, and no interaction of chemical bonding is observed. The CaF 2 -coated LiMn 1/3 Ni 1/3 Co 1/3 O 2 exhibits discharge capacity retention of 98.1% at 0.1C after 50 cycles and high initial discharge capacity of 146.3mAhg −1 at 5C. Furthermore, even at an elevated charge–discharge rate of 5C, capacity retention maintains above 85%. Electrochemical impedance spectroscopy (EIS) shows that the CaF 2 coating can stabilize the surface structure and reduce the charge transfer resistance. The CaF 2 modification has a promising application in improving the performance of layered oxide cathode materials for Li-ion batteries.