Resorcin[4]arene-based cavitand bearing four benzimidazolamido moieties on the upper rim has vase conformation by the clip-type hydrogen bonds of a methanol with CO as well as –NH of a benzimidazolamido unit. These methanol-mediated rigidifications of four benzimidazolamido moieties result in a narrow and deep cavity, and the aromatic protons in the –NH side of benzimidazolyl unit direct to adjacent benzimidazolyl unit. This methanol-mediated cavitand forms weak complexes of n-alkanes by CH/π interaction with the aromatic π surfaces of the walls at low temperature.