Self-assembling peptides and oligonucleotides have given rise to synthetic materials with several applications in nanotechnology. Aggregation of synthetic oligosaccharides into well-defined architectures has not been reported even though natural polysaccharides, such as cellulose and chitin, are key structural components of biomaterials. Here, we report that six synthetic oligosaccharides, ranging from dimers to hexamers, self-assemble into nanostructures of varying morphologies and emit within the visible spectrum in an excitation-dependent manner. Well-defined differences in chain length, monomer modification, and aggregation methods yield glycomaterials with distinct shapes and properties. The excitation-dependent fluorescence in a broad range within the visible spectrum illustrates their potential for use in optical devices and imaging applications. We anticipate that our systematic approach of studying well-defined synthetic oligosaccharides will form the foundation of our understanding of carbohydrate interactions in nature.