AbstractPolystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymer was functionalized with luminescent chlorotricarbonyl rhenium (I) phenanthroline complex in the presence of silver perchlorate. The copolymer-metal complex showed high sensitivity to the solvent system. Different morphologies and dimensions of the rhenium complex within nanosized micelles were controlled by changing the solvent systems. Core-embedded rhenium complex within micelles appear by adding methanol, a poor solvent for the copolymer-metal complex, to the solution of common solvent tetrahydrofuran (THF); the number of the core-embedded rhenium complex and the scale of the micelles are strongly related to the addition of methanol. Moreover, a novel morphology of corona-embedded rhenium complex micelles was prepared by dropping the original THF solution of copolymer-metal complex into water at a low pH value.