The photophysical and electrochemical properties of a novel metallopolymer containing [Re(bpy)(CO)3]+ moieties coordinated to a poly(4-vinylpyridine) polymer chain are reported. Significantly, the release of the metal complexes can be triggered by oxidation or reduction of the rhenium complex. Solvent rapidly binds to the vacant coordination site to give a luminescent product. The redox and photophysical properties of the parent metallopolymer and the released solvated complex are compared. Along with photoemission, the metallopolymer generates significant electrogenerated chemiluminescence upon reduction in the presence of benzoyl peroxide as coreactant.