Lithium-ion batteries are emerging as a major power source for portables appliances such as prime candidate for hybrid electric vehicles (HEVS), plug-in hybrid electric vehicles (PHEVs) and electric vehicles (EVs) for reasons of high energy density, high power density, better cycleability and safety Li and Mn – rich layered compounds of x×Li₂MnO₃ (1-x)×LiMO₂ (M = Mn, Co, and Ni) have drawn a lot of attention due to their high capacity comparing to commercial LiCoO₂. These materials containing the redox active transition metals (Mn, Ni, Co) are reported as structurally integrated materials of two different phases, one with a monoclinic (Li₂MnO₃) structure and the other with a rhombohedral (LiMO₂) phase. These materials can deliver a high discharge capacity of 200–300 mAh/g in the voltage range of 2.0 – 4.8 V and exhibit an excellent cycling performance, which make it an ideal candidate cathode material to realize extensive industrial application, especially in the field of electric vehicle or hybrid electric vehicles. Despite their high specific capacities, these Li and Mn – rich cathode materials have drawbacks that impede their practical applications in advanced Li –ion batteries, such as large irreversible capacity loss in the initial cycle, poor structural stability at high cutoff potential and poor rate capability. These approaches have been reported in some recent studies to improve the electrochemical performance, however the underlying mechanism of such improvement is poorly understood. We will focus our research to understand these issues. In this paper, layered-layered composites were synthesized by the hydrothermal method, as well as the co-precipitation route. X-ray diffraction, scanning electron microscopy, Fourier transform infrared, Raman spectroscopy, high-resolution transmission electron microscope (HR-TEM) were used in conjunction with standard electrochemical techniques (cyclic voltammetry, chronopotentiometry, and electrochemical impedance spectroscopy) for characterizing the electrode materials.