Aiming at the formation of inorganic/organic hybrid gold nanoparticle superstructures, the design and synthesis of acetylene-monofunctionalized multidentate thioether ligands and their ability to stabilize gold nanoparticles are presented. Rather monodisperse gold particles with diameters of about 1 nm are obtained, which are coated by a small number of ligands, each comprising a silyl-protected acetylene. The acetylene is attached at the end of a rigid ethynylene-phenylene unit of variable length, leading to functionalized gold nanoparticles carrying acetylenes at different distances from the nanoparticle surface. These particles are interlinked by diacetylene formation and are investigated by transmission electron microscopy and UV/vis spectroscopy, revealing the formation of nanoparticle aggregates and small superstructures such as dimers or trimers while the nanoparticles themselves retain their integrity. The interparticle distance in small nanoparticle superstructures reflects the ethynylene-phenylene spacer length corroborating the wet chemical interlinking as the origin of these organic/inorganic hybrid structures.