Layered LiFeO₂ with α-NaFeO₂ type structure was synthesized from FeCl₃·6H₂O by hydrothermal reaction at 230 % using aqueous mixed alkaline solution such as LiOH·H₂O-NaOH. The lithium intercalation and deintercalation mechanism was characterized using cyclic voltammetry, and structure identified by X-ray diffraction (XRD), Elctrochemical lithium deintercalation/intercalation reactions were clearly observed between 1.5 and 4.5 V.