Sol–gel synthesized yttria-stabilized zirconia (YSZ) ceramic powders were coated on LiCoO2 cathode particles by a simple mechano-thermal process, calcined at 923K for 10h. The XRD patterns of YSZ-coated LiCoO2 revealed a single-phase hexagonal α-NaFeO2-type structure with R 3 ¯ m symmetry of the core material without any modification. The surface of LiCoO2 particles was coated with a uniform layer of YSZ that had an average thickness of ∼20nm, as observed from TEM images. The different binding energies of O 1s XPS data exhibited the presence of oxygen ions corresponding to the surface coated YSZ and LiCoO2. The galvanostatic cycling studies for the coated materials suggest that 2.0wt.% YSZ-coated LiCoO2 delivered a stable capacity of 160mAhg−1 between 2.75V and 4.4V vs. Li and a good cycle stability of about 142 cycles. The impedance growth was slower for LiCoO2 surface coated with YSZ, when cells were charged at 4.4V and 4.5V. DSC results illustrated that the oxygen evolution exothermic peak at about 458K was significantly smaller for YSZ-coated cathode materials.