A simple one-step method has been developed for the controllable synthesis of hierarchical flower-like alpha-Fe2O3 hollow spheres in a glycerol-ethanol system. It is found that the volume ratio of glycerol/ethanol and reaction time have a significant effect on the morphology of the products. The growth process of alpha-Fe2O3 hollow spheres has been investigated and a possible mechanism is proposed. The alpha-Fe2O3 hollow spheres have a high surface area of 98 m(2) g(-1) and a total pore volume of 0.32 cm(3) g(-1), which exhibit outstanding water treatment performance with high removal capacities toward organic dyes and heavy metal ions. The as-obtained products may have potential applications in water treatment and other related micro-or nanoscale devices. (C) 2013 Elsevier B. V. All rights reserved.