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An ion-selective electrode (ISE) was elaborated based on a calyx[6]arenic ester (C6Es6) as ionophore and PVC as polymer matrix. Potentiometric measurements were performed in standard solutions of Ca²⁺, Mg²⁺, Na⁺, K⁺, NH₄⁺ and Li⁺. The best response was observed for K⁺: slope 52 mV/DpK; linear range from 0.1 mM up to 0.1 M; detection limit of 0.02 mM; potentiometric selectivity coefficients of 0.06 and 0.16 for Na⁺ and NH₄⁺, respectively.