The investigation of hydrophobic interactions under confined conditions is of tremendous interdisciplinary interest. It is shown that based on porous capsules of the type \{(pentagon)\}(12)\{(linker)\}(30) \{(Mo)Mo-5\}(12)\{Mo-2(ligand)\}(30), which exhibit different hydrophobic interiors-achieved by coordinating related ligands to the internal sites of the 30 \{Mo-2\} type linkers-there is the option to study systematically interactions with different uptaken/encapsulated hydrophobic molecules like long-chain alcohols as well as to prove the important correlation between the sizes of the related hydrophobic cavities and the option of water encapsulations. The measurements of 1D- and 2D-NMR spectra (e. g. ROESY, NOESY and HSQC) allowed the study of the interactions especially between encapsulated n-hexanol molecules and the hydrophobic interior formed by propionate ligands present in a new synthesized capsule. Future detailed studies will focus on interactions of a variety of hydrophobic species with different deliberately constructed hydrophobic capsule interiors.