Self-assembly of nanomaterials by wet chemistry methods is a suitable approach for the preparation of engineered structures with novel functionalities. In this work, we study the ability of long-chain amines to direct the growth of a layered nanomaterial, using [Re x Se y Cl z ] clusters as building blocks. The amines link to the clusters as ligands during the synthesis, directing the self-assembly due to their amphiphilic properties, which produces a platelet-shaped 2D material with sizes up to several μm in diameter and thicknesses in the range of 60-80 nm. This is, to the best of our knowledge, the first report on a one-step mild chemistry method for the preparation of 2D structures composed of alternate layers of self-assembled amines and sub-nm clusters of a rhenium chalcogenide. Furthermore, these materials can be used as a suitable source of clusters which then, conveniently released by a simple acid/base reaction, have been successfully incorporated to the surface of graphene. The simple clusters deposition method developed here offers a promising route towards the preparation of hybrid clusters/2D materials with outstanding properties arising from quantum confinement effects combined with high surface areas and the enormous compositional variety of 2D materials and clusters. These hybrids are expected to play a key role in the development of active materials for applications ranging from highly efficient energy storage systems, more active catalysts and upper-sensitivity gas sensors.