The self-assembly process of a supramolecular tris(crown ether) hexagon with [G-1]–[G-3] dendritic dibenzylammonium cations was described. The resulted novel dendrimer systems organized with multiple intermolecular weak interactions were characterized with one-dimensional multinuclear ( 1 H and 31 P) and two-dimensional ( 1 H– 1 H NOESY and ROESY) NMR spectroscopy as well as CSI-TOF-MS spectrometry. It was found that with the introduction of multiple non-covalent intermolecular interactions, supramolecular self-assembly with multiple simple building blocks can effectively form complex higher order dendrimer system. This study implies a simple strategy (i.e., supramolecular self-assembly) to obtain novel dendrimer systems, which have received extensively attention not only for their esthetic beauty but also for their potential utility in a variety of applications where their structures and interiors are of potential benefit.