LiNi0.5Mn0.5O2, LiNi0.475Al0.05Mn0.475O2, and LiNi0.5Mn0.45Ti0.05O2 were prepared via the emulsion drying method. The as-prepared materials showed different degrees of cation mixing. Rietveld refinement of X-ray diffraction data revealed that Al and Ti doping in LiNi0.5Mn0.5O2 was significantly effective to decrease the cation mixing in the octahedral Li layers. The cation mixing consequently affected to the charge and discharge capacities. The irreversible capacity was the smallest for the Al doped LiNi0.5Mn0.5O2, which showed the smallest cation mixing. Al and Ti doped LiNi0.5Mn0.5O2 delivered a stable capacity of about 175mAhg−1 with high reversibility. Such higher capacities were possible to be obtained by the achievement of structural stabilization and enhancement of structural integrity by Al and Ti doping in LiNi0.5Mn0.5O2.