Porous flower-like α-Fe2O3 nanostructures have been synthesized by ethylene glycol mediated iron alkoxide as an intermediate and studied as an anode material of Li-ion battery. The iron alkoxide precursor is heated at different temperatures from 300 to 700°C. The α-Fe2O3 samples possess porosity and high surface area. There is a decrease in pore volume as well as surface area by increasing the preparation temperature. The reversible cycling properties of the α-Fe2O3 nanostructures have been evaluated by cyclic voltammetry, galvanostatic charge discharge cycling, and galvanostatic intermittent titration measurements at ambient temperature. The initial discharge capacity values of 1063, 1168, 1183, 1152 and 968mAhg−1 at a specific current of 50mAg−1 are obtained for the samples prepared at 300, 400, 500, 600 and 700°C, respectively. The samples prepared at 500 and 600°C exhibit good cycling performance with high rate capability. The high rate capacity is attributed to porous nature of the materials. As the iron oxides are inexpensive and environmental friendly, the α-Fe2O3 has potential application as anode material for rechargeable Li batteries.