Crystalline α-Fe2O3 powder was prepared by the mechanical milling of crystalline α-FeOOH at room temperature in air. This result means that crystalline α-FeOOH is dehydrated by mechanical milling at room temperature. The obtained α-Fe2O3 powder worked as a rechargeable electrode material in lithium ion conductive organic electrolytes. The electrodes exhibited high discharge capacities of over 1000mAhg−1 corresponding to 6 Li per α-Fe2O3 at potentials ranging from the open circuit potential to 0.5V (versus Li+/Li) in the first discharging (lithium insertion) process. This suggests that the valence deviation from Fe3+ in α-Fe2O3 to Fe0 may be caused by electrochemical reduction. In contrast, after the first discharge, the electrodes exhibited high charge capacities of more than 700mAhg−1 corresponding to 4.2 Li per α-Fe2O3 in the first charging (lithium extraction) process. The coulombic efficiency at the first cycle was about 70%, suggesting a valence deviation from Fe0 to Fe2+ or Fe3+ caused by electrochemical oxidation.