Novel well-defined diblock copolymers polystyrene-b-poly[benzoic acid N'-(4-vinylbenzoyl)hydrazide dinuclear ruthenium complex] (PS(m)-b-P(DCH-Ru)(n), m = 2076, n = 417, 1024, 2432) are synthesized through two-step sequential nitroxide-mediated radical polymerization (NMRP) and postpolymerization complexation. The block copolymers containing pendant dinuclear ruthenium groups possess an amphiphilic nature. The assembly behavior of the complex block copolymers in both selective solvents acetonitrile and dioxane at various initial concentrations and block compositions were characterized by transirnission electron microscopy (TEM). Spherical micelles and vesicles were observed in acetonitrile and dioxane, respectively. The photoluminescent, electrochemical, and spectroelectrochemical properties of the complex block copolymers in solution were investigated. The solvatochromism in the UV-vis region and electrochromism (EC) in the near-infrared region (NIR) were observed. Aggregates solutions in either acetonitrile or dioxane show quite different electroptical properties from that of the homogeneous solution in DMF, which might be due to spatial-confinement effect of the functional Ru pendent groups in core-shell nanostructures.