Here, we designed a facile solvothermal method to prepare Li1.2Ni0.13Co0.13Mn0.54O2 hollow microspheres with considerable uniformity and monodispersity. In this method, lithium ions and transition metal carbonate have been simultaneously precipitated in the ethanol-polyethylene glycol mixed solvent system to form carbonate precursors, which subsequently transform into self-assembled hollow microspheres by a heat treatment. As cathode material for lithium ion batteries, its unique structure makes for sufficient contact between electrode and electrolyte to provide more reaction sites and shorter paths for Li+ transportation, contributing to remarkable cycling stability and excellent rate capability with improved electrochemical kinetics properties. Specifically, Li1.2Ni0.13Co0.13Mn0.54O2 hollow microspheres achieve a high initial discharge capacity of 287 mAh g−1 at 0.1 C and 234 mAh g−1 at 1 C, with capacity retentions of 85.7% and 81.3% after 100 cycles, respectively. Besides, it exhibits a high rate capacity of 150 mAh g−1 even at 5 C. Moreover, the present synthesis method could also provide an effective and promising strategy for the preparation of high energy density cathode materials for lithium ion batteries.