There is an urgent need to improve the sustainability of the materials we produce and use. Here, we explore what humans can learn from nature about how to sustainably fabricate polymeric fibers with excellent material properties by reviewing the physical and chemical aspects of materials processing distilled from diverse model systems, including spider silk, mussel byssus, velvet worm slime, hagfish slime, and mistletoe viscin. We identify common and divergent strategies, highlighting the potential for bioinspired design and technology transfer. Despite the diversity of the biopolymeric fibers surveyed, we identify several common strategies across multiple systems, including: (1) use of stimuli-responsive biomolecular building blocks, (2) use of concentrated fluid precursor phases (e.g., coacervates and liquid crystals) stored under controlled chemical conditions, and (3) use of chemical (pH, salt concentration, redox chemistry) and physical (mechanical shear, extensional flow) stimuli to trigger the transition from fluid precursor to solid material. Importantly, because these materials largely form and function outside of the body of the organisms, these principles can more easily be transferred for bioinspired design in synthetic systems. We end the review by discussing ongoing efforts and challenges to mimic biological model systems, with a particular focus on artificial spider silks and mussel-inspired materials.