Macroporous Li1.2Mn0.54Ni0.13Co0.13O2 cathode materials with high crystallinity and hexagonal ordering are synthesized by aerogel template followed by solid state reaction. High discharge capacities of 244.0 mA h g−1 and 153.9 mA h g−1 are obtained for the Li-rich layered oxide synthesized at 800 °C at current densities of 200 mA g−1 and 2000 mA g−1 between 2.0 V and 4.8 V. Increasing the synthesis temperature to 900 °C, the macroporous Li1.2Mn0.54Ni0.13Co0.13O2 delivers a high discharge capacity of 220.2 mA h g−1 at a current density of 200 mA g−1 with a capacity retention of 89.1% after 50 cycles, 129.8 mA h g−1 at a current density of 2000 mA g−1 and almost no capacity fading after 120 cycles. The diffusion coefficients of Li+ in the Li-rich layered oxide determined by galvanostatic intermittent titration technique are in the range of 5.0 × 10−18−8.0 × 10−14 cm2 s−1. Electrochemical impedance spectroscopy indicates that the macroporous structure with good particle contact of the layered oxide can improve its rate capability and cyclic stability.