With well-defined molecular architectures and geometries, natural fibrous nanostructures possess super physicochemical and biologic properties, allowing performing a variety of specific functions in living systems and also serving as building blocks in material science. Endeavor has been made to extract biologic nanomaterials to retain their nanostructures and properties. Chitin nanofibrils, one of the most abundant polysaccharide nanomaterials in nature, were directly extracted from crab shells through a green deprotonation-assisted liquid exfoliation procedure. In contrast to traditional chemical-etching exfoliation process, this approach not only minimized the structural variation of chitin molecules, but also gave a production yield as high as similar to 60%. Moreover, their aqueous re-dispersibility after freezing/air/thermal drying offered the facileness of hybridization with other two-dimensional nanomaterials, e.g. graphene and transitional metal dichalcogenides. Such hybrids combined the advantages of their building blocks, including flexibility, toughness, conductivity and photo-thermal properties, being able to serve for applications in all-solid-state supercapacitors and photothermal converters desired in wearable circuits, biodegradable electronics and smart actuators.