Understanding the thermodynamics of non‑polar functionalities’ inclusion within cyclodextrins and cucurbiturils paves the way for the design of new macrocyclic receptors, enables their wider industrial application, and provides insights into the hydration of lipophilic guests and cavities of these receptors. To shed light on the influence of guest structure, temperature, and solvent on the complexation of amphiphilic aliphatic and aromatic compounds and their hydrophobic analogs with cyclodextrins and cucurbiturils, the corresponding reactions were characterized microcalorimetrically in a wide temperature range (278 ≤ T / K ≤ 338), and the structure of the resulting complexes was investigated by NMR spectroscopy. The affinity of cucurbiturils towards all guests, with the exception of 1‑naphthol in water, is noticeably higher compared to cyclodextrins with an equal number of monomeric subunits. This is in all cases due to extremely exothermic complexation with glycoluryl receptors, whereby systematic calorimetric studies of inclusion also indicate the entropically less favorable dehydration of the cucurbituril cavity. Reaction heat capacities are negative for most complexation reactions in water, which leads to pronounced temperature enthalpy-entropy compensation. The observed ΔrH°(T) and ΔrS°(T) dependencies are largely due to changes in the organization of water around nonpolar guest functionalities and can be interpreted by their cosmotropic effect on the solvent at lower, and kaotropic at higher temperatures. This significantly affects the thermodynamics of inclusion within cyclodextrins, which is in most cases entropically controlled at 278 K. The inclusion of aliphatic derivatives is entropically favored compared to their aromatic analogues in the case of β-cyclodextrin, and enthalpically favored in the case of cucurbit[7]uril. This results in higher affinity for aliphatic guests in both cases. Unlike in water, the complexation reactions in formamide and ethylene glycol are enthalpically controlled, and ΔrH° almost independent of temperature. Consequently, although solvophobic inclusion is not a water-limited phenomenon, the temperature dependence of the corresponding thermodynamic complexation parameters is due to its specific solvation properties.