Layered Li[Ni(1−x)/3Mn(1−x)/3Co(1−x)/3Cr x ]O2 materials with x =0, 0.01, 0.02, 0.03, 0.05 are prepared by a solid-state pyrolysis method. The oxide compounds were calcined with various Cr-doped contents, which result in greater difference in morphological (shape, particle size and specific surface area) and the electrochemical (first charge profile, reversible capacity and rate capability) differences. The Li[Ni(1−x)/3Mn(1−x)/3Co(1−x)/3Cr x ]O2 powders were characterized by means of X-ray diffraction (XRD), charge/discharge cycling, cyclic voltammetry, and SEM. XRD experiment revealed that the Li[Ni(1−x)/3Mn(1−x)/3Co(1−x)/3Cr x ]O2 (x =0, 0.01, 0.02, 0.03, 0.05) were crystallized to well layered α-NaFeO2 structure. The first specific discharge capacity and coulombic efficiency of the electrode of Cr-doped materials were higher than that of pristine material. When x =0.02, the sample showed the highest first discharge capacity of 241.9mAhg−1 at a current density of 30mAg−1 in the voltage range 2.3–4.6V, and the Cr-doped samples exhibited higher discharge capacity and better cycleability under medium and high current densities at room temperature.