Syntheses and chelation of tailored biodegradable polymers to rhenium for medicinal applications are described. A group of bifunctional ligand-initiators consisting of a chelating end for metal complexation and a hydroxyl end suitable to initiate polymerization was utilized in the ring-opening polymerization of l-lactide. The resulting biodegradable ligand-polymers were equipped with a tridentate donor set to coordinate specific metal ions. All synthesized compounds were characterized by IR spectroscopy, 1D/2D NMR spectroscopy and MALDI-TOF mass spectrometry, confirming successful polymerization and coordination to the [Re(CO)(3)](+) core. The pliability of designing application-specific polymers with respect to the nature of the metal ion facilitates extending the application of these biodegradable polymers to early detection of diseases (imaging) and radiotherapy of cancers.