The α-Fe2O3 powders composed of different flower-like or yarn-like clusters are prepared by a thermal decomposition process of iron alkoxide precursors, which are obtained via a simple reaction between iron acetylacetonate and ethylene glycol in an oil bath. X-ray diffraction, thermogravimetric analysis, scanning electron microscopy, Brunauer–Emmett–Teller measurement, and galvanostatic cell cycling are employed to characterize the structures and electrochemical performance of these α-Fe2O3 samples. The results show that these α-Fe2O3 electrodes have stable cycling performance with a reversible capacity of over 800mAhg−1 after 40 cycles. The sample with optimized structure shows the best rate performance with a high capacity of 622mAhg−1 at the current density of 4687mAg−1. The experimental results suggest that such an α-Fe2O3 powder is a promising anode material for high energy-density lithium-ion batteries.