Chitin, ap olymer composed of b(1-4)-linked Nacetyl-glucosamine monomers,a nd its partially deacetylated analogue chitosan,a re abundantb iopolymersw ith outstandingm echanical as well as elastic properties. Their degradation products,c hitooligosaccharides (COS), can trigger the innate immune response in humans and plants.B othm aterial and biological propertiesa re dependent on polymer length, acetylation,a sw ell as the pH. Withoutw ell-defined samples, ac omplete molecular descriptiono ft hese factors is still missing. Automated glycan assembly (AGA)e nabled rapid access to synthetic well-defined COS. Chitin-cellulose hybrid oligomers were prepared as importantt ools for as ystematic structural analysis. Intramolecular interactions, identified by molecular dynamics simulations and NMR analysis,u nderscore the importanceo ft he chitosana mino group for the stabilization of specific geometries.