Lithium iron oxides (Li x Fe y O z ) have been synthesized using LiOH and α-FeOOH by a solid-state method at various temperatures (200–800°C). The lithium iron oxide obtained at 200°C is composed of three types of structure namely, α-LiFe5O8, β-LiFe5O8, and a trace of cubic α-LiFeO2. It exhibits not only a high initial discharge capacity 215mAhg−1, but also excellent cycling retention from the 11th to the 50th cycle (95%) between 1.5 and 4.5V. On the other hand, the powder obtained at 800°C has a well-developed, single α-LiFeO2 phase and gives a very poor cycle performance below 5mAhg−1 under the same test conditions. It is also found that lithium iron oxide obtained at 200°C is first transformed into the spinel LiFe5O8 phase and is then converted into the tetragonal LiFeO2 phase after a long-term cycling. It is suggested that the tetragonal LiFeO2 phase might assist the stabilization of the original lithium iron oxide structure on cycling.