Nature employs flexible molecules to bind anions in a variety of physiologically important processes whereas supramolecular chemists have been designing rigid substrates that minimize or eliminate intramolecular hydrogen bond interactions to carry out anion recognition. Herein, the association of a flexible polyhydroxy alkane with chloride ion is described and the bound receptor is characterized by infrared and photoelectron spectroscopy in the gas phase, computations, and its binding constant as a function of temperature in acetonitrile.