A donor acceptor-structured diruthenium complex, 1(PF6)(4), that contains an electron-deficient bridging ligand and electron-rich distal diarylamines modified with long aliphatic chains has been synthesized. By varying the solvent environments and assembly conditions, we obtained three different self-assembled nanostructures of 1(PF6)(4), including zero-dimensional nanospheres, one-dimensional nanofibers, and thin films with interconnected nanowire networks. These structures were investigated by scanning electron microscopy, transmission electron microscopy, dynamic light scattering, X-ray diffraction, and atomic force microscopy (AFM) analysis. Conductive AFM analysis shows that the nanowire networks exhibit a high conductivity of 0.023 S/cm and an enhanced photoconductivity of 0.59 S/cm under visible light irradiation.