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)Mo5}12{Mo2(ligand)}30, which exhibit different hydrophobic interiors—achieved by coordinating related ligands to the internal sites of the 30 {Mo2} 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.