Sub-micron sized LiNi0.8Co0.15Al0.05O2 cathode materials with improved electrochemical performance caused by the reduced cationic disordering in Li slab were synthesized through a solid state reaction routine. In a typical process, spherical precursor powder was prepared by spray drying of a uniform suspension obtained from the ball-milling of the mixture of the starting raw materials. Then the precursor powders were pressed into tablets under different pressures and crushed into powder. The pressing treated powders were finally calcinated under oxygen atmosphere to obtain the target cathode materials. XRD investigation revealed a hexagonal layered structure without impurity phase for all samples and significant increase in the diffraction intensity ratio of I(003)/I(104) was observed. Rietveld refinement further confirmed the reduced cationic disordering in Li slab by such pressing treatment, and the smallest disordering was observed for sample S4 with only 1.3% Ni ions on Li lattice position. The electrochemical testing showed an improvement in electrochemical behavior for those pressing treated samples. The calculation of diffusion coefficients using EIS data showed improved Li diffusion coefficient after pressing treatment. The sample S4 presented a diffusion coefficient of 4.36 × 10-11 cm2·s-1, which is almost 3.5 times the value of untreated sample.