The assembly of Rh(CO)(2)Cl(amine) via molecular orbital symmetry interactions, resulting in the formation of one-dimensional molecular wires, has been discovered. The assembly behavior was quite dependent on the type of amine. The interchain distances and optical properties could be controlled by changing the length of the alkyl chain in the amine. We believe that this discovery can be applied not only to preparing more diverse one-dimensional molecular wires via the introduction of predesigned amines but also to gaining a deeper understanding of the physical properties of molecular metals.