The fabrication of an ultra-dense, highly periodic nanoparticle array from a soft template is one of the most important issues in the fields of material science and nanotechnology. To date, block copolymer (BCP) structures have been primarily used as templates for fabricating highly periodic nanoparticle arrays with high areal densities. Herein, we demonstrate for the first time the use of a supramolecular dendrimer assembly for the formation of a highly ordered nanoparticle array with a high areal density of similar to 20 Tdot/in(2), four times larger than that of the currently reported BCP-based nanoparticle arrays. By the simple thermal annealing of a dendrimers containing a metal precursor between two flat, solid substrates, a hexagonal array of small gold nanoparticles (with a diameter of similar to 1.6 nm and center-to-center distance of similar to 5.3 nm), oriented normal to the bottom, was achieved. Density functional theory calculations demonstrated that the gold cation strongly bound to the head group of the dendrimer. This structure served as a building block for self-assembly into a stable cylindrical structure. We anticipate that this study will lead to the creation of a large family of supramolecular dendrimers that can be utilized as soft templates for creating periodic, ultra-dense nanoparticle arrays.