Layered LiNi0.2Mn0.2Co0.6O2 phase, belonging to a solid solution between LiNi1/2Mn1/2O2 and LiCoO2 most commercialized cathodes, was prepared via the combustion method at 900°C for a short time (1h). Structural, electrochemical and magnetic properties of this material were investigated. Rietveld analysis of the XRD pattern shows this compound as having the α-NaFeO2 type structure (S.G. R-3m; a =2.8399(2)Ǻ; c =14.165(1)Ǻ) with almost none of the well-known Li/Ni cation disorder. SQUID measurements clearly indicate that the studied compound consists of Ni2+, Co3+ and Mn4+ ions in the crystal structure. X-ray analysis of the chemically delithiated Li x Ni0.2Mn0.2Co0.6O2 phases reveals that the rhombohedral symmetry was maintained during Li-extraction, confirmed by the monotonous variation of the potential–composition curve of the Li//Li x Ni0.2Mn0.2Co0.6O2 cell. LiNi0.2Mn0.2Co0.6O2 cathode has a discharge capacity of ∼160mAhg−1 in the voltage range 2.7–4.3V corresponding to the extraction/insertion of 0.6 lithium ion with very low polarization. It exhibits a stable capacity on cycling and good rate capability in the rate range 0.2–2C. The almost 2D structure of this cathode material, its good electrochemical performances and its relatively low cost comparing to LiCoO2, make this material very promising for applications.