Polystyrene-block-poly(4-vinylpyridine) was functionalized with a chlorotricarbonyl rhenium(I) diimine complex. Compared to the metal-free copolymer, the copolymer-metal complex exhibited different morphologies, which are highly sensitive to the solvent used for spin-coating and the surface properties of the substrates. Well-defined cylindrical or spherical domains were observed. Due to its ionic nature, the poly(4-vinylpyridine)--rhenium complex block could also serve as a template for subsequent deposition of cadmium sulfide nanoparticles by electrostatic attraction. The pattern of the deposited nanoparticles was found to be the replica of the block copolymer underneath, and their presence on the film surface was confirmed by X-ray photoelectron spectroscopy.