1 H and 13C N.m.r. studies and conformational analysis have been performed on the methyl glycosides of ten 1,2- and 1,3-linked disaccharides in which the glycosidic linkages have different stereochemical surroundings. Conformational analysis, using the HSEA-approach, indicates a number of protonoxygen and proton–proton interactions, resulting, inter alia, in downfield and upfield shifts of anomeric proton signals, respectively. The 13C n.m.r. glycosylation shifts obtained have been used to simulate spectra of 1,3-linked α- and β-D-glucan.