15-Membered tri-olefinic azamacrocycles as end-groups of phosphorus-containing dendrimers from generation 1 to 4 are used for obtaining Pt nanoparticles in mild conditions; remarkable and unprecedented branched supramolecular assemblies composed of dendrimers and coalesced Pt nanoparticles are obtained, which become larger for higher dendrimer generations, affording for the first time a very unique organization of organic dendritic structures interweaved with inorganic dendritic structures.