The kinetics of Li-ion deintercalation in Li1.12[Ni0.5Co0.2Mn0.3]0.89O2 samples is studied by electrochemical impedance spectroscopy (EIS) and galvanostatic intermittent titration technique (GITT) during the first charge process. The impedance response of Li1.12[Ni0.5Co0.2Mn0.3]0.89O2 largely depends on the open-circuit voltage (OCV) of the cell, showing that the mechanism of electrode kinetics under different potentials is dominated by different electro-chemical reactions. Meanwhile, the equivalent circuit is proposed to simulate the EIS data, deducing the circuit elements (R i and C i) which are normally modeled as a multistep process of electro-chemical reactions. The change trend of R sf (the resistance of SEI film) and R ct (the charge-transfer resistance) in the first charge process are exactly similar. The C dl (double-layer capacitance) as a function of voltage gradually increases, particularly after 4.5V. The maximum of C sf (the film capacitor) observed in the first charge process shows that the most intensive ionic fluxes will appear when the Li1.12[Ni0.5Co0.2Mn0.3]0.89O2 electrode reach to the transient equilibrium at different levels of deintercalation. To study the faster capacity fading of Li1.12[Ni0.5Co0.2Mn0.3]0.89O2 during the first charge process, the Li-ion diffusion coefficient (D Li) is also calculated based on the results of EIS and GITT.