Recently, the integration of spinel and layered structure received significant attentions to improve the electrochemical performance of the Lithium and manganese rich oxide material. In this work, Lithium-rich, Li4Mn5O12–Li2MnO3 composite is synthesized by the Sol-gel method. The structural and electrochemical performances of the composite materials are analyzed. X-ray diffraction result confirms the formation of spinel Li4Mn5O12 and layered Li2MnO3 mixed phase. Scanning electron microscopy image depicts the presence of an elongated particle with an average size of 50–60 nm. Transmission electron microscopy result clearly shows the existence of spinel and layered phase. Raman measurement result indicates the presence A1g, E2g and F2g vibration modes of MnO6 octahedron. Li4Mn5O12–Li2MnO3 composite cathode delivers a first discharge capacity of 318 mA h g−1 at 0.1C rate and retains the discharge capacity of 209 mA h g-1 at the 50th cycle. The capacity retention of the composite cathode is 89% after 50 charge-discharge cycles. Formation of a hybrid composite structure enhances the capacity, rate capability and structural stability of the Li4Mn5O12–Li2MnO3 cathode material.