Supramolecular architectures, based on synthetic peptides or DNA, are the essence of modernbionanotechnology. Carbohydrates, the most abundant biopolymers in Nature tend to form hierarchicalarchitectures. Limited access to pure and well-defined carbohydrates hampered the molecular levelunderstanding of polysaccharides, preventing the production of tailor-made materials. AutomatedGlycan Assembly produces now well-defined natural and unnatural oligosaccharides for detailedstructural characterization. Defined glycans can assemble into supramolecular materials with differentmorphologies, depending on their chemical structure. Here, we describe how synthetic oligo- andpolysaccharides help to establish structure–property correlations to guide the development of novelpolysaccharide materials