Biopolymers are synthesized by living organisms in a variety of sophisticated structures that serve as inspiration for advanced materials. One significant challenge in processing olysaccharides is their non-thermoplastic nature and insolubility in common solvents. Chemical modifications enable cellulose, chitin and chitosan derivatives to be easily soluble in a range of solvents and robustly electrospun into nanofibrous, micro-porous and meso-porous fibers, shealth-core hybrid, hierarchical multi-scale structures1-3. Self-assembling of nanocelluloses also generate nanofibers and 3D networks of new fibrous structures4, super-absorbent hydrogels5 and amphiphilic aerogels.6 These cellulose aerogels engineered by either approach have shown to exhibit super-absorbency, wet-resiliency, dry strength and tunable amphiphilic-to-hydrophobic characteristics. While these two approaches lead to fibers and aerogels with similar morphologies, their crystalline structures, thermal behavior and chemical functionalities are distinctively different. Coupling these two offers further unique properties. Biological nanomaterial innovations can offer versatile solutions to meet future demand in advanced sustainable materials while reduce negative environmental impact from our food and energy systems. ACKNOWLEDGMENTS Funding from USDA-NIFA, NSF, NIH, CAPES, California Rice Research Board, Chevron and AgTech Innovation Center and research contributions from coauthors below and J. Zhou are greatly appreciated. REFERENCES 1. Liu, H., Y.-L. Hsieh, J. Polym Sci, Polym Physics, 40(18):2119 (2002). 2. Du, J.,Y.-L. Hsieh, Cellulose, 16(2): 247 (2009). 3. Lu, P., Y.-L. Hsieh, J. Mem Sci, 348 (1-2):21 (2010). 4. Jiang, F., S. Han, Y-L. Hsieh, RSC Advances, 3(30): 12366 (2013). 5. Jiang, F., Y.-L. Hsieh, J. Materials Chem A, 2: 6337 (2014). 6. Jiang, F., Y.-L. Hsieh, ACS App Materials & Interfaces, 9 (3), 2825 (2017).