The NiO thin film was deposited on the stainless and single crystal Si substrate by the dip-coating combined with thermal treatment. Thermal decomposition behavior of gel precursor, the structure, morphology and electrochemical properties of NiO thin film were characterized by TG-DSC, XRD, SEM, cyclic voltammetry and the constant current charge/discharge technology. The results show that the gel completely decomposes at 430°C to form the nanocrystalline NiO gradually and its crystal structure becomes integrity and particles largen as the increasing of the sintering temperature. The NiO film sintered at 600°C exhibits smooth surface, uniform, compact and free of cracks. At the cut-off voltage of 0-3V and the current density of 0.01 mA/cm2, its first discharge special capacity is 1285mAh/g and remains 650mAh/g after 300 cycles. In addition, the special capacity of NiO thin film still remains above 300mAh/g at large current density of 0.04 mAh/g after 300cycles exhibiting excellent electrochemical performance.