By a facile LiNO 3 flux method, lithium manganese oxide composites (xLi 4 Mn 5 O 12 ∙yLi 2 MnO 3 ) were synthesized using a hierarchical organization precursor of manganese dioxide. Li 4 Mn 5 O 12 and Li 2 MnO 3 have spinel and rocksalt structures, respectively. The lithiation and structural transformation from the precursor to the composites occurred topotactically from exterior toward interior in the precursor particle with the increase of reaction time, and the composites had core-shell spinel@rocksalt structures in addition to the original hierarchical core-shell organization. The electrochemical measurements at 50°C after 50 cycles confirmed that a typical spinel@rocksalt cathode had higher capacity retention (87.1%) than that with the composition close to the stoichiometric spinel (64.6%), indicating the Li 2 MnO 3 shell can improve cycling stability for the composite electrode at elevated temperature.