Pyrogallol[4]arenes form stable hydrogen-bonded nanocapsules that have unique properties that may make them suitable for diverse applications, such as catalysts and molecular transporters. Little is known about the behavior of the interior of these new materials in solution, and by using the solvent-dependent properties of 1-(9-anthryl)-3-(4-dimethylaniline) propane (ADMA), the inner phase properties of the hexamers are investigated. Steady-state and dynamic spectrofluorometric results are in agreement, are consistent with solid-state studies, and indicate that the majority of ADMA is sequestered in an extended conformation with the crystallization solvent. The conformational flexibility of ADMA is attributed to lower capsule occupancies (similar to 50%, i.e., 1 molecule per 2 capsules, one occupied and one empty) relative to our previous study with pyrene butyric acid (occupancy of 150%, i.e., 1.5 molecules per capsule) in which the probe was restricted within a nanocapsule. The nature of the encapsulated ADMA complexes are found to change with time, as there is either fluorophore leaching from the capsule or endo-exo-capsule solvent exchange. However, the choice of crystallizing solvent (ethyl acetate or acetonitrile) and PgC(n) alkyl tail (C-6 or C-10) does not influence experimental outcomes. These research findings give a better understanding of the encapsulation versatility of these unique supramolecular assemblies and the protective nanopockets that can exist for guest molecules.