A series of benzylic thioether-based dendron-type organic ligands for the stabilization of ultrasmall gold nanoparticles was synthesized. The ligands are capable of enwrapping gold particles of a diameter of 1–1.5 nm in a 1:1 ligand-to-particle ratio. After initial success with unfunctionalized ligands, a single, remote chemical functional unit was introduced, demonstrating that monofunctional gold nanoparticles can be used for the fabrication of superstructures of precisely arranged gold nanoparticles via “click” chemistry. The nanoparticles were bench-stable in both dry state as well as dispersed in organic solvent for a period of several months and were characterized by TEM, UV–vis, TGA and 1H-NMR.