Using solution based processing route, we have successfully synthesized xLi(Ni 0.8 Co 0.15 Mg 0.05 )O 2 –(1−x)Li[Li 1/3 Mn 2/3 ]O 2 (0.0 ≤ x ≤ 1.0) cathode materials for lithium rechargeable batteries. The phase formation behavior of these cathode materials is characterized by X-ray diffraction measurements. The Galvanostatic charge–discharge characteristic of these cathodes is reported in various cut-off voltage limits. When these composite cathodes are charged to 4.8 V, electrochemical extraction of lithium takes place from active (Li[Ni 0.8 Co 0.15 Mg 0.05 ]O 2 ) as well as inactive (Li[Li 1/3 Mn 2/3 ]O 2 ) components. Good cycleability of these cathodes is obtained when cycled in the cut-off voltage limits of 4.6–3.0 V. The cycleability of these cathodes are deteriorated when charged above 4.8 V and deep discharged up to 1.2 V followed by repeated cycling in these voltage limits. Based on the analyses of impedance spectra at various charge and discharge states, the probable reasons for such findings are discussed.