Anion recognition has continuously attracted significant attention due to its important role in environmental and biological sciences. Here, we have designed and synthesized an electron-deficient fluorinated leaning pillar[6]arene 1 that contains two tetrafluoro-benzene units. The electron-deficient fluorinated leaning pillar[6]arene 1 is capable of selectively recognizing iodide anions to form a host–guest complex with 1 : 1 stoichiometry driven by anion–π interactions. Our work ascribes this selective recognition to the preorganization of macrocycles, suitable cavity size, and the effect of anion–π interactions. The innovative application of this macrocycle offers us a new avenue for the design of selective receptors for anions and electron-deficient macrocyclic arenes.