We report a solution NMR and X-ray crystallographic study on the anion affinity of all-cis 1,2,3,4,5,6-hexafluorocyclohexane, which has only recently become synthetically accessible. Our results suggest that the interaction exhibits preferential 1 : 1 stoichiometry, while its strength is only moderate (e.g. Ka = 400 M-1 in acetone for Cl-) and depends mainly on the size of the anion and the dielectric constant of the solvent.