The application of Mott–Schottky (MS) analysis to electrochemical impedance data recorded for microparticulate deposits of archaeological ceramic materials is described. Upon attachment to paraffin‐impregnated graphite electrodes in contact with aqueous acetate buffer at pH 4.75, impedance data in potential ranges with and without the occurrence of faradaic processes provide MS graphs used to characterize ceramic samples. The methodology is applied to the discrimination between local and foreign workshops of a series of overpainted and black‐glazed ware fragments recovered in the archaeological site of Pyrgi in Santa Severa (Rome, Italy), corresponding to the Etruscan culture. The robustness of the MS‐based classification is further supported by complementary optical microscopy (OM) and X‐ray powder diffraction (XRPD) analyses.