The subunits controlled alpha-Fe2O3 hollow spherical particles were synthesized with a facile hydrothermal method. The two-dimensional single-crystalline nanosheets associated with the one-dimensional single-crystalline nanorods self-assembled into the three-dimensional hierarchical flower-like mesoporous alpha-Fe2O3 hollow spheres by adjusting the relative amount of cetyltriethylammnonium bromide in the reaction system. The electrochemical measurements indicated that the three-dimensional hierarchical flower-like alpha-Fe2O3 hollow spherical particles contained a remarkable specific capacity, a lower irreversible capacity loss and an excellent rat performance for their higher specific surface and mesoporous structure. The discharge capacity of the electrodes made by the three-dimensional hierarchical flowerlike alpha-Fe2O3 hollow spheres was retained at 875 mAh g(-1) even after 100 charge-discharge cycles at the current densities of 200 mA g(-1). (C) 2018 Elsevier B.V. All rights reserved.