Polysaccharides offer a wealth of biochemical and biomechanical functionality that can be used to develop new biomaterials. In mammalian tissues, polysaccharides often exhibit a hierarchy of structure, which includes assembly at the nanometer length scale. Furthermore, their biochemical function is determined by their nanoscale organization. These biological nanostructures provide the inspiration for developing techniques to tune the assembly of polysaccharides at the nanoscale. These new polysaccharide nanostructures are being used for the stabilization and delivery of drugs, proteins, and genes, the engineering of cells and tissues, and as new platforms on which to study biochemistry. In biological systems polysaccharide nanostructures are assembled via bottom-up processes. Many biologically derived polysaccharides behave as polyelectrolytes, and their polyelectrolyte nature can be used to tune their bottom-up assembly. New techniques designed to tune the structure and composition of polysaccharides at the nanoscale are enabling researchers to study in detail the emergent biological properties that arise from the nanoassembly of these important biological macromolecules.