Biological materials have robust hierarchical structures capable of specialized functions and the incorporation of natural biologically active components, which have been finely tuned through millions of years of evolution. These highly efficient architectural designs afford remarkable transport and mechanical properties, which render them attractive candidates for flexible electronic sensing technologies. This review provides a comprehensive overview of the fundamental aspects and applications of biological materials for flexible electronic devices and discusses various classes of biological materials by describing their unique structures and functions. We discuss the effect of the biological activity of biological materials on the improved properties in detail, because this effect overcomes the limited bioavailability and restricted morphology of materials generally encountered in traditional flexible electronic devices. We also summarize various approaches for the design and functionalization of natural materials and their applications in flexible electronic devices for use in biomedical, electron, energy, environmental and optical fields. Finally, we provide new insights and perspectives to further describe trends for future generations of biological materials, which are likely to be critical components (building blocks or elements) in future flexible electronics.