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Sensitivity is a key parameter for an analytical method, because it determines the analytical performance of the method in analyzing low concentration samples. In electroanalytical methods, charging current causes interference with the accurate measurement of the faradaic current and restricts sensitivity and detection limit. How to separate faradaic current from charging current in an electrochemical system has been a challenge in the last several decades. Chemometrics has speeded up the development of electrochemical analysis and with the help of chemometric methods such as multivariate curve resolution alternating least squares (MCR-ALS), iterative target transformation factor analysis (ITTFA) and alternating trilinear decomposition (ATLD) contribution of charging current from total current can be eliminated. In this review, we will focus on applications of chemometrics to separation of charging current from total current to obtain net faradaic current for improving sensitivity of electroanalytical methods based on the literature in this field. Keywords: Chemometrics, Electroanalytical methods, Sensitivity, Detection limit, Charging current, Faradaic current