A metastable form of LiFeO2 with alpha-NaFeO2-type structure (layered LiFeO2) was synthesized directly from alpha-FeOOH or FeCl3 . 6H(2)O by hydrothermal reaction at 230 degrees C using aqueous mixed-alkaline solutions such as LiOH . H2O-KOH or LiOH . H2O-NaOH. Highly crystallized samples could be obtained by a one-step process. The yield of the layered LiFeO, strongly depends on the composition of the starting mixture. Preliminary tests on electrochemical lithium deintercalation/intercalation show poor performance between 4.5 and 1.5 V.