In this work, we designed a facile in-situ template-sacrificial route to prepare LiNi1/3Co1/3Mn1/3O2 hollow microspheres with an average diameter of 2.0μm for the first time through using porous spinel Mn1.5Co1.5O4 hollow microspheres as the template, the formation of which could originate from a synergic effect of the contraction and adhesion action generated during the oxidative decomposition of the Mn0.5Co0.5CO3 precursors. The walls of the as-prepared hollow microspheres are ~300nm in thickness, and composed of numerous primary particles with size of hundreds of nanometers. The as-synthesized nanocrystal-assembled hollow structure showed singnificantly enhanced electrochemical performance with high capacity, excellent cycling stability and good rate capability, compared with the bulk counterparts, when used as a cathode material for Li ion batteries (LIBs), which can be attributed to the unique nano/micro hierarchical structure. Specifically, the resulting LiNi1/3Co1/3Mn1/3O2 hollow microspheres achieve a high discharge capacity of 157.3mAhg−1 at 0.2C after 100 cycles and 120.5mAhg−1 at 0.5C after 200 cycles with an excellent cycle life. Interestingly, it exhibits a high rate capacity of 114.2mAhg−1 even at a current of 1Ag−1 (5C). On the basis of this work, the pesent preparation strategy could provide an effective and general approach to improve the cyclability and rate capability of high-capacity cathode materials with hollow interiors for the application of LIBs.