The specific functionalization of hexachlorocyclotriphosphazene with one function different from the five others was used for the synthesis of bifunctional dendrimers having one protected amine linked to the core and either 5 phosphines or 10 phosphine imines (P,N ligands) as terminal groups. In the latter case, reaction with PdCl 2 (COD) affords the corresponding complexes of the P,N ligands. All compounds were characterized by multinuclear NMR, and particularly by 31 P NMR, which proved to be a very precious tool for the characterization of sophisticated structures such as dendrimers.