The layered material of Ce-doped LiNi1/3Mn1/3Co1/3O2 with α-NaFeO2 was synthesized by a co-precipitation method.X-ray diffraction (XRD) showed that Ce-doped LiNi1/3Mn1/3Co1/3O2 had the same layered structure as the undoped LiNi1/3Mn1/3Co1/3O2.The scanning electron microscopy (SEM) images exhibited that the particle size of Ce-doped LiNi1/3Mn1/3Co1/3O2 was smaller than that of the undoped LiNi1/3Mn1/3Co1/3O2.The Ce-doped LiNi1/3Mn1/3Co1/3O2 samples were investigated on the Li extraction/insertion performances through charge/discharge,cyclic voltammogram (CV),and electrochemical impedance spectra (EIS).The optimal doping content of Ce was x=0.02 in the LiNi1/3-xMn1/3Co1/3CexO2 samples to achieve high discharge capacity and good cyclic stability.The electrode reaction reversibility was enhanced,and the charge transfer resistance was decreased through Ce-doping.The improved electrochemical performances of the Ce-doped LiNi1/3Mn1/3Co1/3O2 cathode materials were attributed to the addition ofCe4+ ion by stabilizing the layer structure.