Lithium manganese oxides have attracted much attention as cathode materials for lithium secondary batteries in view of their high capacity and low toxicity. In this study, layered manganese oxide (δ-K x MnO2) has been synthesized by thermal decomposition of KMnO4, and four lithium manganese oxide phases have been synthesized for the first time by mild hydrothermal reactions of this material with different lithium compounds. The lithium manganese oxides were characterized by powder X-ray diffraction (XRD), inductively coupled plasma emission (ICPE) spectroscopy, and chemical redox titration. The four materials obtained are rock salt structure Li2MnO3, hollandite (BaMn8O16) structure α-MnO2, spinel structure LiMn2O4, and birnessite structure Li x MnO2. Their electrochemical properties used as cathode material for secondary lithium batteries have been investigated. Of the four lithium manganese oxides, birnessite structure Li x MnO2 demonstrated the most stable cycling behavior with high Coulombic efficiency. Its reversible capacity reaches 155mAhg−1, indicating that it is a viable cathode material for lithium secondary batteries.