Two different kinds of hollow spherical materials Li1.2Mn0.54Ni0.13Co0.13O2 which are assembled by the nanoplate-shaped particles and the quasi-sphere shaped particles, have been prepared through the homogeneous precipitation of metal oxalate precursor and subsequent solid state reaction with lithium nitrate. X-ray diffraction (XRD) pattern shows the two as-prepared samples have a good layered structure and solid solution characteristic. As the lithium-ion battery cathode, the as-prepared sample exhibits an initial discharge capacity of 286.4 mAh g−1 at 0.1 C between 2.0 and 4.8 V, and a discharge capacity of 240.9 mAh g−1 can be retained after 50 cycles. The structure of hollow spherical material is assembled with nanoplate-shaped particles, which is beneficial for improving the rate performance. It is due to the shortened transmission distance for Li+ from the cathode materials to electrolyte. At the charge–discharge rate of 1.0 C, a stable discharge capacity of 170.5 mAh g−1 also can be reached after 112 cycles with capacity retention of 86.2%. Meanwhile, the relationship of structure and electrochemical performance is also discussed in detail.