Carbohydrates, also known as glycans in biological systems, are omnipresent in nature where they as glycoconjugates occur as oligo‐ and polysaccharides linked to lipids and proteins. Their three‐dimensional structure is defined by two or three torsion angles at each glycosidic linkage. In addition, transglycosidic hydrogen bonding between sugar residues may be important. Herein we investigate the presence of these inter‐residue interactions by NMR spectroscopy in D2O/[D6]DMSO (70:30) or D2O and by molecular dynamics (MD) simulations with explicit water as solvent for disaccharides with structural elements α‐d‐Manp‐(1→2)‐d‐Manp, β‐d‐GlcpNAc‐(1→2)‐d‐Manp, and α‐d‐Glcp‐(1→4)‐β‐d‐Glcp, all of which have been suggested to exhibit inter‐residue hydrogen bonding. For the disaccharide β‐d‐GlcpNAc‐(1→2)‐β‐d‐Manp‐OMe, the large extent of O5′⋅⋅⋅HO3 hydrogen bonding as seen from the MD simulation is implicitly supported by the 1H NMR chemical shift and 3JHO3,H3 value of the hydroxy proton. In the case of α‐d‐Glcp‐(1→4)‐β‐d‐Glcp‐OMe, the existence of a transglycosidic hydrogen bond O2′⋅⋅⋅HO3 was proven by the presence of a cross‐peak in 1H,13C HSQC‐TOCSY experiments as a result of direct TOCSY transfer between HO3 of the reducing end residue and H2′ (detected at C2′) of the terminal residue. The occurrence of inter‐residue hydrogen bonding, albeit transient, is judged important for the stabilization of three‐dimensional structures, which may be essential in maintaining a conformational state for carbohydrate–protein interactions of glycans to take place in biologically important environments.