Self-sorting of a mixture of partial cone 2,4-bis[(2-pyridylmethyl)oxy]-(1,3)-p-tert-butylcalix[4]crown-6, hexadecafluoro-1,8- diiodooctane and CsI in EtOH produces a crystalline ?supramolecular salt?. Similar calix/CsI/iodofluorocarbon adducts are shown to exist also in solution. In a prototypical study, a combination of this calixcrown and liquid octafluoro-1,4-diiodobutane acts as an effective ?binary host? system for the selective extraction of CsI from aqueous to fluorous phase.