Unfortunately, simple ion transfer between two immiscible solutions is practically impossible for highly hydrophilic compounds like chloride, fluoride, and sulphate ions. In such situations, it is possible to use facilitated ion transfer by adding an ionophore to the aqueous or organic phase , , but generally not in the case of fluoride and sulphate ions. No known compound would enable the transfer of these highly hydrophilic ions across the phase boundary in a three-phase electrode system. In this work, we used ion pair receptors whose specific structure is designed to enable the extraction of salts from the aqueous phase even in the case of very hydrophilic sulphate and chloride ions , . Ion pair receptors are compounds capable of simultaneous and cooperative binding of cations and anions. Three functional parts can be distinguished in the receptors 5FSQC6 and CF3SQC6, studied in the present work: a cation-binding domain (benzo-18-crown-6 ether), an anion-binding domain (squaramide) and a unit assuring both the lipophilicity and increased acidity to the anion-binding domain (pentafluorophenyl or 3,5bis(trifluoromethyl)phenyl groups). Using the properties of dialkoxy squarates for sequential amidation, individual units can be introduced using proper amines, creating asymmetric amides. This property enabled the synthesis of receptors 5FSQC6 and CF3SQC6 by first introducing a unit imparting lipophilicity, creating monoamides M1 or M2. In the next step, the benzo-18-crown-6 ether unit was introduced, obtaining receptors 5FSQC6 and CF3SQC6 with yields of 80 and 79%, respectively (Scheme 1. ). domain, i.e. to the benzo-18-crown-6 ether. This type of crown ether is selective towards potassium cations and binds this cation by six etheric oxygen atoms . The crown ether is an integral part of the anion-binding functionality. The binding of a potassium cation in the crown ether reduces the electron density on the phenyl ring, further increasing the acidity of the squaramide protons and, consequently, increasing the binding of anions . This paper is the first time this kind of ion pair compound is applied both as an ionophore and as a redox probe in the organic droplet using a (TPE) setup. We show that it is possible to selectively transfer highly hydrophilic anions, such as sulphate and fluoride, across the phase boundary. We also demonstrate that the receptor forming an ion pair transfers anions better than its individual parts. DFT (density functional theory) calculations were performed to help understand the data. Finally, the receptor was used in potentiometry to investigate their utility in ion-selective electrodes.