Various wt.% of Al2O3 derived from methoxyethoxy-alumoxane (MEA-alumoxane) were coated by a simple mechano-thermal method on the LiCoVO4 particles, which were synthesized by a citric acid–urea polymeric method. Powder XRD patterns confirmed that the prepared LiCoVO4 crystalline sample had an inverse spinel structure when heated at 773K for 5h in air and the LiCoVO4 materials coated with Al2O3 showed no evidence of secondary phase peaks. TEM images of LiCoVO4 identified that the nanosized particles ranged ∼100–120nm and Al2O3 coating had an average thickness of ∼20nm over the fine particle of LiCoVO4. XPS binding energy data indicated that the presence of two different types O 1s ions corresponds to alumina and core LiCoVO4 material. The charge and discharge study indicated that the 0.5wt.% Al2O3 derived from MEA-alumoxane coated material delivered an initial discharge capacity of 68mAhg−1 at 3.0–4.5V and the cycle stability after 20 cycles was stable without any drastic capacity fade normally exhibited by inverse spinel materials. The dQ/dV versus voltage plots revealed that the slower impedance growth for the Al2O3 surface coated LiCoVO4 cathode material.