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α,α′,α″,α′″-meso-Tetrahexyltetramethyl-calix[4]pyrrole is easily obtained as a single diastereomer in a one-pot reaction. It exhibits enhanced solubility in organic solvents, including aliphatic solvents, relative to its parentmeso-octamethylcalix[4]pyrrole (1). Somewhat surprisingly, the tetrahexyl derivative2complexes with tributylmethylammonium chloride in chloroform more strongly than does1as shown by NMR titrations. However,1and2exhibit comparable complexation strength in extraction experiments, the difference between the NMR and extraction results being attributed to the effect of organic-phase water in the extraction systems. Mass-action analysis indicates the formation of the predominant complex TBMA+(1or2)Cl−in both NMR and extraction systems, and equilibrium constants are reported. x-Ray crystal structures were obtained for the free ligand2and its complex with tetramethylammonium chloride. The free ligand crystallises in the 1,3-alt conformation with equatorial hexyl arms. In the chloride complex with2in its cone conformation, the hexyl arms adopt an axial orientation, enveloping the anion. DFT calculations show this binding conformation to be the most stable, mostly owing to destabilising steric interactions involving the pyrrole C–H and alkyl C–H groups positioned equatorially. [ABSTRACT FROM AUTHOR]