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 obserbed between 1.5 and 4.5 V.