β-FeOOH prepared with an enhanced hydrolysis method had been subjected to H+/Li+ exchange with various lithium salts in ethanol for various duration. The effects of the kind of lithium salt used and the duration of ionic exchange on the composition, the crystalline structure, and the electrochemical properties of the prepared powders were investigated. It was found that α-LiFeO2 can be prepared from β-FeOOH by an ionic exchange reaction with LiOH in ethanol at 85°C. α-LiFeO2 powders so prepared show electrochemical active properties with reversible capacity of 65–80mAhg−1. The in situ XRD patterns of the cycled α-LiFeO2 cathode revealed that the crystalline structure remains unchanged while the lattice of cubic decreases and increases periodically upon charge/discharge cycling. The results of XANES suggest that the electrochemical reaction of the Fe3+/Fe2+ redox couple occurs as the prepared α-LiFeO2 electrode is charge/discharge cycled.