LiNiO2 thin films were fabricated by RF magnetron sputtering. The microstructure of the films was determined by X-ray diffraction and field-emission scanning electron microscopy. The electrochemical properties were investigated with a battery cycler using coin-type half-cells. The LiNiO2 thin films annealed below 500°C had the surface carbonate. The results suggest that surface carbonate interrupted the Li intercalation and deintercalation during charge/discharge. Although the annealing process enhanced the crystallization of LiNiO2, the capacity did not increase. When the annealing temperature was increased to 600°C, the FeCrNiO4 oxide phase was generated and the discharge capacity decreased due to an oxygen deficiency in the LiNiO2 thin film. The ZrO2-coated LiNiO2 thin film provided an improved discharge capacity compared to bare LiNiO2 thin film suggesting that the improved electrochemical characteristic may be attributed to the inhibition of surface carbonate by ZrO2 coating layer.