The effect of the electric field on the conformational behavior of model compounds for glycosidic linkages, 2-methoxytetrahydropyran (MTHP) with axially and equatorially oriented methoxy groups has been investigated by the ab initio molecular orbital method. The geometry of rotamers about the glycosidic C-O bond was determined by gradient optimization at the 6-31G* level. The potential of rotation about the glycosidic C-O bond has been calculated using the 6-31+G* basis set in an electric field. The 6-31G* optimized geometries were used to calculate energy differences between the AGT, ATG, AGG, EGT, ETG, and EGG conformers with 6-31G*, 6-31+G*, 6-31+G**, 6-311++G*, and MP2/6-31G* basis sets. The electric field has been applied in various directions and strengths. The calculations revealed that strong electric fields influence the topology of the rotational; potential energy. At all levels of theory, the electric field has shown to have a significant effect on the relative energies of conformers. This effect is so pronounced that in fields of E(x) = 0.01, E(x) = -0.01, and E(z) = -0.01 au the axial-equatorial equilibrium is reversed. Whereas in gas-phase axial MTHP is preferred by 1.08 kcal/mol, in the presence of these fields, contrary to the anomeric effect, equatorial MTHP is favored by 1.63, 1.14, and 3.48 kcal/mol, respectively. Electric fields also influence the relative stability of conformers in both MTHP anomers. In the field of E(y) = -0.01 au, the TG conformers are found to be favored over GT in both anomers, contrary to the exo-anomeric effect which prefers the GT conformers. All larger basis sets give relative energies which agree fairly well with the 6-31+G* results. These results suggest that strong external fields present on membrane surfaces might considerably influence conformational equilibria around the glycosidic linkages of carbohydrate portions of membrane glycoconjugates and thus their overall shape. They also imply that conformations not found in gas-phase or solution equilibria might be of importance in the biological activity of membrane bound molecules.