Natural metal-organic complexes have gained much attention due to their self-assembly behaviors and photochemical properties. They perform various biological processes, including catalysis, anti-oxidation, molecular transport, and structural organization. Recently, the bio-inspired metal-phenolic complexes have been widely adopted as molecular scaffolds and redox-active molecules for the fabrication of functional materials. This review focuses on recent studies on the applications of metal-polyphenol complexes as bioinspired materials to build functional biomaterials possessing unique physical and chemical properties. Metal-phenolic coordination provides a simple fabrication route to complex and hierarchical structures as found in metal-ligand complexes in nature, leading to assembled supramolecular materials and robust interfaces of metal species with polyphenols. Furthermore, the metal-polyphenol chemistry features the versatile biochemical and structural functions of metal species through complexation with polyphenols as biocompatible ligands. This article is concluded with a discussion on the redox properties of metal-phenolic coordination potentially useful for biomedical applications.