An ion-pair receptor, 1, containing both cation- and anion-recognizing sites, has been synthesized and characterized. Single-crystal X-ray diffraction structural studies and H-1 NMR spectroscopic analyses confirmed that 1 forms stable 1:1 complexes with CsF in solution and in the solid state in spite of the large separation enforced between the receptor-bound anion and cation. In 9:1 CDCl3/CD3OD, binding of fluoride anion within the calix[4]pyrrole core of 1 was not observed in the absence of a cobound cesium cation; however, it was seen in this solvent mixture under conditions where a Cs+ cation was bound to the crown ether-strapped calix[4]arene subunit.