Hierarchical Mn2O3 microsphere is obtained by rapid microwave hydrothermal synthesis. Large specific surface area with mesoporous is characterized. High specific capacity of 921.6 mAh g−1 is reached at 200 mA g−1. Continual enhancement of interface Li-storage brings an abnormal high capacity. High capacity of 525 mAh g−1 is obtained at 1000 mA g−1 after 500 cycles.