Li(Ni0.8Co0.1Mn0.1)O2 cathode materials were synthesized by solid-state reaction route. Single-phase layer structure with hexagonal unit cell having R 3 ¯ m symmetry was obtained and the average particle size was around 6μm. Electrochemical studies showed single redox reaction and a maximum charging capacity of ∼140mAhg−1 was obtained. Ex situ structural studies by X-ray diffraction and Raman scattering at various stages of charging and discharging showed that the host layered structure is maintained throughout the electrochemical lithiation–delithiation processes in the 3–4.5V range with systematic change in the lattice parameters. First discharge capacity was 132mAhg−1 and the capacity retention was ∼86% after 20 charge–discharge cycles.