Rapid microwave hydrothermal synthesis is carried out to obtain hierarchical Mn2O3 microsphere through a self-assembled process within 30 minutes. All the raw materials used is nontoxicity without any template or polymer and the side-products are all small molecules which abide by the pricnciple of environmental protection. After the following solid state reaction, the as-prepared Mn2O3 powders can still keep the hierarchical morphology of micro sphere which is consisted of small primary particles and secondary slices. The sample obtained at 600 degrees C With high crystallinity, large specific surface area and mesoporous exhibits best electrochemical performances. High specific capacity of 921.6 mAh g(-1) could be reached at a current density of 200 mA g(-1). An interesting phenomenon with abnormal capacity increasing appears which could be ascribed to the continual enhancement of interface Li-storage. Thus, high specific capacity of about 525 mAh g(-1) is obtained at high current density of 1000 mA g(-1) after 500 cycles. Furthermore, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) are performed to further study the hierarchical Mn2O3 anode material. It is revealed that such rapid microwave synthesis without any contamination is considered as a promising way to obtain hierarchical manganese oxides as anode material for applications. (C) 2016 Elsevier Ltd. All rights reserved.