In this paper, 1H NMR spectroscopy, isothermal titration calorimetry, X-ray crystallography and other characterization methods were used to investigate the interaction modes of tetramethyl cucurbit[6]uril(TMeQ[6]) and three benzimidazole derivatives in an aqueous solution-solid state. The results showed that the aromatic ring moieties in the three derivatives all entered the cavity of TMeQ[6] and their substituents were located at the port of TMeQ[6], forming 1:1 host-guest inclusion complexes. The crystal structures showed that the aromatic part of the benzimidazole derivatives interacted with the cavity of TMeQ[6] via hydrogen bond interactions and the N atoms on the benzimidazole ring formed hydrogen bonds with the carbonyl oxygen of TMeQ[6]. The ion-dipole interactions between [ZnCl4]2− and TMeQ[6] formed supramolecular self-assembly entities.