LiCo2/3Ni1/6Mn1/6O2 layered oxide was synthesized by the combustion method that led to a crystalline phase with good homogeneity and low particles size. The structural properties of the prepared positive electrode material were investigated by performing XRD Rietveld refinement. Practically no Li/Ni mixing was detected evidencing that the studied compound adopts almost an ideal α-NaFeO2 type structure. The Li||LiCo2/3Ni1/6Mn1/6O2 cell showed a discharge capacity of 199mAhg−1 when cycled in the 2.7–4.6V potential range while the best cycling performances were recorded when the upper cut off is fixed at 4.5V. Structural changes in Li x Co2/3Ni1/6Mn1/6O2 with lithium electrochemical de-intercalation were studied using X-ray diffraction. This study clearly shows the existence of a solid solution domain in the 0.1< x <1.0 composition range while for x =0.1, a new phase appears explaining the decrease of the electrochemical performance when the cell is cycled at high upper cut off voltage.