A rechargeable lithium-ion batteries cathode LiNi0.5Mn0.5O2 with hollow nano/micro hierarchical microspheres (LNMO-HS) is prepared. LNMO-HS with diameters of about 1μm is composed of approximately 100nm primary nanoparticles. The initial discharge capacity of LNMO-HS cathode is as high as 181.5mAhg−1 at 1C between 2.5 and 4.5V. The corresponding capacity retention is 96.3% during 100 charge and discharge cycles. The reversible discharge capacities are 152.2 (10C) and 134.6mAhg−1 (15C), respectively. After 1000 cycles at 15C, the capacity retention of LNMO-HS cathode is up to 95.5%. The superior rate capability and cyclability of LNMO-HS cathode can be attributed to the distinctive hollow nano/micro hierarchical microspherical structures. It could not only effectively reduce the paths of Li ions diffusion, increase contact area between electrodes and electrolyte but also buffer the volume changes during Li ions intercalation/deintercalation processes.