Flower-like hematite (α-Fe2O3) has been successfully prepared by heat-treatment from the iron(III)-oxyhydroxide precursor, which is obtained by the hydrolysis of FeCl3 solution in the presence of NaClO. In this process, no templates or catalysts are required. SEM and TEM characterizations confirm that micro-flowers are composed of several dozen self-assembled nanopetals with the thickness of about 20nm. On the basis of the morphology investigations in time-dependent experiments, the possible growth mechanism of the flower-like α-Fe2O3 is proposed, which is similar to a two-stage growth process. Furthermore, as an anode electrode material for rechargeable lithium-ion batteries, the flower-like α-Fe2O3 exhibits excellent electrochemical performance, which can be attributed to the high surface area induced by the flower-like structure, the short lithium diffusion length and the restriction of volume change of the Li+ insertion/extraction.