The layered Li-rich Li[Li 0.13 Mn 0.464 Ni 0.203 Co 0.203 ]O 2 cathode material was successfully synthesized via a hydrothermal treatment on the precursor method. X-ray diffraction spectrometry (XRD) and scanning electron microscopy (SEM) were used to characterize the structure and micromorphology of the materials. Meanwhile, charge-discharge test and electrochemical impedance spectroscopy (EIS) were employed to explore its electrochemical performance. The results indicate that the Li[Li 0.13 Mn 0.464 Ni 0.203 Co 0.203 ]O 2 material possesses a layered α-NaFeO 2 structure and exhibits excellent electrochemical performance. The initial discharge capacity is 235.9 mAh•g −1 in the voltage range of 2.0-4.8 V at 0.1 C. And it exhibits the capacity retention of 94.1% after 50 cycles. The hydrothermal treatment not only shortens the calcination time, but also can greatly improve the electrochemical performance of the material.