The nature of the dendrimer-mycophenolic acid (MPA) complex was investigated by H-1 NMR and 2D NOESY spectroscopy. The H-1 NMR analysis proved that the water-soluble supramolecular structure of the complex was formed based on ionic interactions between dendrimers and MPA molecules on the surface as well as hydrophobic interactions/hydrogen-bond interactions in the interior pockets of dendrimers. The 2D NOESY analysis predicted the localization of MPA molecules in the pockets of dendrimers and gave information on the detailed interactions between dendrimer scaffolds and MPA molecules in the interior. Further solubility and release studies investigated the physicochemical properties of the dendrimer-MPA complexes. These results showed that the host-guest chemistry of dendrimer-MPA complexes proposed by NMR techniques explains the solubilization and release behavior of MPA in the presence of PAMAM dendrimers well. The general host-guest chemistry of the dendrimer-drug complex is promising for the development of new drug delivery systems.