The self-assembly behavior of 1,3-alternate p-tert-butylthiacalix[4]arene tetra-methyleneoxycarboxylic acid (I) and 1,3-alternate p-H-thiacalix[4]arene tetra-methyleneoxycarboxylic acid (II) in ethanol, acetone and in the existence of 4,4′-bipyridine were studied by single-crystal X-ray diffraction methods. Compound I maintains almost the same tubular shape molecular structure and the unique water inclusion property ([I ∩ 2H₂O]) in the three different crystallization media because of the steric hindrance posed by the t-butyl groups. While for compound II, its molecular structure and water inclusion property are susceptible to the crystallization medium due to the absence of the t-butyl groups.