A rigid C(3v)-symmetrical host molecule, syn-1,3,5-tris(2-hydroxy-5-pentylphenyl)-2,4,6-trimethylbenzene, was readily obtained via Suzuki coupling and thermal atropisomerization. The host molecule effectively associated with various saccharides by multipoint hydrogen bonds, whereas its anti-atropisomer and analogue lacking in methyl groups showed much weaker association with saccharides. Thermodynamic analyses suggested that the difference of the association strength was caused by entropic factors.