Collision-induced dissociation (CID) of sodiated glucose was investigated using electronic structure calculations and resonance excitation in a low-pressure linear ion trap. The major dissociation channels in addition to desodiation are dehydration and C₂H₄O₂ elimination reactions which the barrier heights are near to or lower than the sodiation energy of glucose. Dehydration reaction involves the transfer of the H atom from the O2 atom to the O1 atom, followed by the cleavage of the C1–O1 bond. Notably, α-glucose has a dehydration barrier lower than that of β-glucose. This difference results in the larger branching ratio of dehydration reactions involving α-glucose, which provides a simple and fast method for identifying the anomeric configurations of glucose. The C₂H₄O₂ elimination starts from the H atom transfer from the O1 atom to the O0 atom, followed by the cleavage of the C1–O0 bond. These results were further confirmed by experimental study using ¹⁸O-isotope-labeled compounds. Both the experimental data and theoretical calculations suggest that the dehydration reaction and cross-ring dissociation of sodiated carbohydrates mainly occur at the reducing end during low-energy CID.