Novel Li1.2Mn0.5Co0.25Ni0.05O2 microcube is prepared through a simple binary template method. After calcined at 800 °C, lithium and nickel are permeated into the cathode material and a well-crystallized Li-rich layered oxide is obtained. Furthermore, hollow circle cube architecture is formed due to the decomposing of the carbonate. As a cathode material for lithium ion batteries (LIBs), the oxide with such architecture can deliver high initial discharge capacity of 272.9 mAh g−1 at a current density of 20 mA g−1. High reversible discharge capacities of 208 mAh g−1 and 110 mAh g−1 are obtained at a current density of 200 mA g−1 and 2000 mA g−1, respectively. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) are performed to further study the hollow Li1.2Mn0.5Co0.25Ni0.05O2 microcube. It is remarkable that such architecture makes the Li-rich layered oxide Li1.2Mn0.5Co0.25Ni0.05O2 a promising cathode material for LIBs.