Li[Li0.2Mn0.54Ni0.13Co0.13]O2 as a cathode material for Li-ion battery has been successfully prepared by co-precipitation (CP), sol–gel (SG) and sucrose combustion (SC) methods. The prepared materials were characterized by XRD, SEM, BET and electrochemical measurements. The XRD result shows that the Li[Li0.2Mn0.54Ni0.13Co0.13]O2 materials prepared by different methods all form a pure phase with good crystallinity. SEM images and BET data present that the SC-material exhibited the smallest particle size (ca. 0.1μm) and the highest surface area (7.4635m2 g−1). The tap density of SC-material is lower than that of CP- and SG-materials. The result of rate performance tests indicates that the SC-material showed the best rate capability with the highest discharge capacity of 178mAhg−1 at 5.0C, followed by SG-material and then CP-material. However, the cycling stability of SC-material tested at 0.1 and 0.5C is relatively poor as compared to that of SG-material and CP-material. The result of EIS measurements reveals that large surface area and small particle size of the SC-electrode result in more SEI layer formation because of the increased side reactions with the electrolyte during cycling, which deteriorates the electrode/electrolyte interface and thus leads to the faster capacity fading of the SC-material.