LiCoO2 thin film was successfully prepared by the PVP sol-gel method. The films were applied for evaluating chemical diffusion coefficients of Li+ ion ((D) over tilde) in LiCoO2 matrix, which was estimated by three different electrochemical methods, such as cyclic voltammetry, (CV), the potentiostatic intermittent titration technique (PITT), and electrochemical impedance spectroscopy (EIS). The apparent chemical diffusion coefficient of Li+ ion in LiCoO2 film was preliminarily calculated to be 4.2 x 10(-13) cm(2) s(-1) from CV. EIS exhibited that the charge-transfer resistance was dramatically decreased at 3.90 V vs. Li/Li+ during a charge state, indicating that Li+ ion was easily extracted from LiCoO2 matrix at this potential. (D) over tilde obtained from EIS ranged from 10(-13) to 10(-12) cm(2) s(-1) at various electrode potentials. From PITT, (D) over tilde were estimated to be similar to 10(-12) cm(2) s(-1) at various electrode potentials. (C) 2004 The Electrochemical Society.