Hybrid nanostructures are interesting materials for numerous applications in chemistry, physics, and biology, due to their novel properties and multiple functionalities. Here, we present a synthesis of metal-semiconductor hybrid nanostructures composed of nontoxic I-III-VI semiconductor nanoparticles and gold. Copper indium sulfide selenide (CuInSSe) nanocrystals with zinc blende structure and trigonal pyramidal shape, capped with dodecanethiol, serve as an original semiconductor part of a new hybrid nanostructure. Metallic gold nanocrystals selectively grow onto vertexes of these CuInSSe pyramids. The hybrid nanostructures were studied by transmission electron microscopy, energy dispersive X-ray analysis, X-ray diffraction, and UV-Vis-absorption spectroscopy, which allowed us conclusions about their growth mechanism. Hybrid nanocrystals are generated by replacement of a sacrificial domain in the CuInSSe part. At the same time, small selenium nanocrystals form that stay attached to the remaining CuInSSe/Au particles. Additionally, we compare the synthesis and properties of CuInSSe-based hybrid nanostructures with those of copper indium disulfide (CuInS 2 ). CuInS 2 /Au nanostructures grow by a different mechanism (surface growth) and do not show any selectivity.