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This work is focused on the design and preparation of polymer inclusion membranes (PIMs) for potential applications for stannous cation sequestration from water. For this purpose, the membranes have been synthesized employing two polymeric matrices, namely, polyvinylchloride (PVC) and cellulose triacetate (CTA), properly enriched with different plasticizers. The novelty here proposed relies on the modification of the cited PIMs by selected extractants expected to interact with the target cation in the membrane bulk or onto its surface, as well as in the evaluation of their performances in the sequestration of tin(II) in solution through chemometric tools. The composition of both the membrane and the solution for each trial was selected by means of a D-Optimal Experimental Design. The samples such prepared were characterized by means of TG-DTA, DSC, and static contact angles investigations; their mechanical properties were studied in terms of tensile strength and elastic modulus, whereas their morphology was checked by SEM. The sequestering ability of the PIMs toward stannous cation was studied by means of kinetic and isotherm experiments using DP-ASV. The presence of tin in the membranes after the sequestration tests was ascertained by μ-ED-XRF mapping on selected samples., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)