We have synthesized a series of polystyrene-block-poly(4-vinylpyridine)s (PS-b-PVP) to which luminescent tricarbonyl(2,2'-bipyridyl)rhenium(I) complexes were attached. The rhenium complexes could induce the self-assembly of the copolymers into nanosized micelles with different shapes and dimensions, depending on the block size distribution of the copolymers and the solvent system being used. In general, spherical micelles were observed when methanol, a nonsolvent for the polystyrene block, was added to a copolymer solution in dichloromethane. Micellization was observed when the added methanol concentration was approximately 30%. When toluene, a nonsolvent for the polyvinylpyridine) block, was added to the copolymer solution in dichloromethane, micelles with different interesting shapes were observed. For copolymers with larger PVP block size, spherical micelles were observed. When the relative block size of the PVP block was reduced, the micelles gradually changed to disk or vesicle structures and then to rodlike structures. The rhenium complex can act as a luminescent probe in tho resulting nanosized micelles and provide sufficient contrast for electron microscopic studies. Significant, changes in luminescence spectra were observed after the micellization.