Abstract: FeF₃-coated LiLi_0.2Mn_0.54Ni_0.13Co_0.13O₂ cathode materials were synthesized via a wet chemical process followed by solid state reaction. The physical properties of the prepared samples were analyzed by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The results indicate that the surface of cathode particles was covered by FeF₃ film (about 5~20 nm thick). The FeF₃-coated LiLi_0.2Mn_0.54Ni_0.13Co_0.13O₂ cathode delivers higher coulombic efficiency, better rate capability and longer cycle life when compared with raw cathode. A high capacity retention of 94.2% (190.6 mAh·g^-1) after 100 cycles at 0.5 C rate is obtained by the FeF₃-coated LiLi_0.2Mn_0.54Ni_0.13Co_0.13 O₂ cathode. In addition, the electrochemical impedance spectra reveal that the enhanced electrochemical properties of the surface-modified samples are due to the presence of FeF₃ coating layer, which can suppress side reaction between the LiLi_0.2Mn_0.54Ni_0.13Co_0.13O₂ particles and electrolytes, and further stabilize LiLi_0.2Mn_0.54Ni_0.13Co_0.13O₂ structure.