LiNi1/3Mn1/3Co1/3O2 with LiF additives was prepared by a spray dry process, and characterized by XRD, SEM, TEM, ICP, XPS, EIS and charge–discharge testing. Although some of the LiF was lost during the preparation, the remaining LiF existed on the surface of the LiNi1/3Mn1/3Co1/3O2 particles and had little influence on its structure. The LiF addition could not only promote the combine of the particles and increase the tap density of the material, but also effectively improve the cyclic performance of LiNi1/3Mn1/3Co1/3O2 at high cutoff voltages (up to 4.7V) and at a high current density. The EIS results suggest that the LiF presence could significantly suppress the increase in the charge transfer resistance that occurred during the charged storage state or after long cycling, which should be related to the improvement on the electrochemical properties.