Protein‐metal interactions—traditionally regarded for roles in metabolic processes—are now known to enhance the performance of certain biogenic materials, influencing properties such as hardness, toughness, adhesion, and self‐healing. Design principles elucidated through thorough study of such materials are yielding vital insights for the design of biomimetic metallopolymers with industrial and biomedical applications. Recent advances in the understanding of the biological structure–function relationships are highlighted here with a specific focus on materials such as arthropod biting parts, mussel byssal threads, and sandcastle worm cement. Protein–metal interactions were traditionally regarded for their role in metabolic processes. Nowadays, they are also known to enhance the performance of certain biogenic materials, influencing properties such as hardness, toughness, adhesion, and self‐healing. In this Review, recent advances in the understanding of the biological structure–function relationships are highlighted.