AbstractPolyoxopalladates (POPs) are a class of self‐assembling palladium‐oxide clusters that span a variety of sizes, shapes and compositions. The largest of this family, {Pd84}Ac, is constructed from 14 building units of {Pd6} and lined on the inner and outer torus by 28 acetate ligands. Due to its high water solubility, large hydrophobic cavity and distinct 1H NMR fingerprint {Pd84}Ac is an ideal molecule for exploring supramolecular behaviour with small organic molecules in aqueous media. Molecular visualisation studies highlighted potential binding sites between {Pd84}Ac and these species. Nuclear Magnetic Resonance (NMR) techniques, including 1H NMR, 1H Diffusion Ordered Spectroscopy (DOSY) and Nuclear Overhauser Spectroscopy (NOESY), were employed to study the supramolecular chemistry of this system. Here, we provide conclusive evidence that {Pd84}Ac forms a 1 : 7 host‐guest complex with benzyl viologen (BV2+) in aqueous solution.