It was found with the help of spectrophotometry, IR spectroscopy, X-ray phase analysis, and thermogravimetry, that new supramolecular structures in the β-cyclodextrin–β-resorcylic acid system are generated as a result of a spontaneous exothermic process. It was proven that the inclusion complexes of the host–guest type with a 1:1 ratio between β-cyclodextrin and the molecular form of β-resorcylic acid (or its monovalent anion) are formed through van der Waals interactions of the aromatic ring of β-resorcylic acid with the inner hydrophobic cavity of β-cyclodextrin. It was shown that partial displacement of water molecules from the inner cavity of the cyclic oligosaccharide and complete immersion of β-resorcylic acid molecule inside it occur in this case; thermal stability of β-resorcylic acid increases.