Self-assembly of neutral Rhenium(I)-based supramolecules via orthogonal-bonding approach in an one-pot process under solvothermal condition is achieved in high yields. Various types of assemblies can be created based on the nuclearity of the luminophore including bimetallic, trimetallic materials, rectangles, cages and boxes. The structural characteristics of the ligands as well as the metal centers present in the neutral supramolecules allow easy tuning of their emission properties. The neutral supramolecular structures are unique in their well-defined shapes and sizes and would be expected to function as a host with a large internal cavity sizes generated by the tailored ligands. Hence, the presence of photophysical properties and the cavity sizes of these neutral supramolecules make them intriguing hosts for guest molecules. This monograph provides an overview of the structures, properties and applications of neutral rhenium(I)-based supramolecules.