Anomalous glycosylation shift values of the signals for C-1 (the anomeric carbon atom) and C-2 (the glycosyloxylated carbon atom) were sometimes observed for 2- O-β- d-glycopyranosyl (or -β- d-xylopyranosyl)-β- d-glucopyranosides, whereas no remarkable displacements of the other sugar-carbon signals were observed in these cases. This can be explained in terms of change of the orientation of the glycosyl linkages, owing to strong, steric interaction between the 2- O-glycosyl group and the 1- O-aglycon (or -sugar) group. Various 2- O-glycosylated α- and β- l-arabinopyranosides were synthesized. In the case of α- l-arabinopyranosides, the processes of 2- O-β- d-glucosylation, -β- d-xylosylation, and -α- l-arabinosylation resulted in unexpected, upfield shifts of the C-3, -4, and -5 signals, together with displacement of the C-1 and -2 resonances. Furthermore, significant alteration of the values of 3 J H1,H2 and 1 J C1,H1 was also observed for the 2- O-glycosylated α- l-arabinopyranoside moiety, indicating an increase in the contribution of the 1 C 4 conformation of the glycosylated α- l-arabinopyranoside in these cases. On the other hand, no remarkable variation in the signals of C-3, -4, and -5, or in the 3 J H1,H2 and 1 J C1,H1 values, was found for 2- O-α- l-rhamnosylation, except for 4-epihederagenin-3-yl 2- O-α- l-rhamnopyranosyl-α- l-arabinopyranoside. In the present study, such unusual 2- O-glycosylation shifts were not encountered for the 2- O-glycosylation of β- l-arabinopyranosides.