Biological systems harness the properties of metal complexes through metalloproteins that absorb and emit light, transfer electrons, and serve as magnetic centers and catalysts in natural materials. While these properties are desirable to incorporate into synthetic polymers, too, basic design principles for the generation of safe and effective synthetic metallopolymers are often lacking. Our research is concerned with polymeric metal complexes, a bio-inspired molecular design that features site-isolated metal centers in well-defined polymer environments. We incorporate metal complex functionalities into biomaterials—ones that sit at the intersection of green chemistry and materials for medicine—to understand how metals and polymers mutually affect each other during synthesis and in terms of their properties. For instance, we have incorporated iron and boron dibenzoylmethane (dbm) centers into poly(lactic acid) (PLA), a biodegradable and biocompatible polymer that can be synthesized from lactide, a bio-derived monomer, using solvent-free methods. Dbm is a classic ligand in inorganic chemistry with reported anticancer activities and, in this respect, can be beneficial rather than toxic to incorporate into materials. Iron tris(dbm) plays multiple roles, as a dbm protecting group, initiator and built-in catalyst for PLA synthesis, and as a chromophore, and responsive, cleavable link in the resulting degradable star polymer structure. Red-orange iron tris(dbmPLA) can be decolorized with acid treatment, forming metal-free dbmPLA macroligands. The presence of metals and dbm may affect degradation and bioactivity. Boron dbm materials, in contrast, are of interest for their impressive optical properties. They are one- and two-photon absorbers, they are intensely fluorescent with high quantum yields, and their emission color can be sensitive to the local environment. Certain boron biomaterials also display oxygen-sensitive phosphorescence and can serve as sensors. Highlights of our work with polymeric dibenzoylmethane complexes will be presented.