In order to satisfy the requirement of high energy density and long cyclability for lithium-ion batteries, Fe2+ self-doped hierarchical flower-like mesoporous Fe2O3 nanosheets with a high specific surface area of 120.57 m2 g−1 are prepared through ultrafast microwave assisted systhesis and post calcination. The obtained Fe2O3 exhibits a superior electrochemical performance on lithium storage (2000 mA h g-1 at 400 mA g-1 up to 300 cycles and 1750 mA h g−1 at 1 A g-1 even up to 1000 cycles) and excellent cycling stability, which are likely to be associated with the specific structure and increased electronic conductivity contributed from Fe2+ defects. These findings not only enormously improve the electrochemical property of Fe2O3 anode, but offer a new perspective for designing of distinctive nanomaterials for various energy devices.