Dehydration of water from surface Mg2+ is most likely the rate-limiting step in the dolomite growth at low temperature. Here, we investigate the role of polysaccharide in this step using classical molecular dynamics (MD) calculations. Free energy (potential of mean force, PMF) calculations have been performed for water molecules leaving the first two hydration layers above the dolomite (104) surface under the following three conditions: without catalyst, with monosaccharide (mannose), and with oligosaccharide (three units of mannose). MD simulations reveal that there is no obvious effect of monosaccharide in lowering the dehydration barrier for surface Mg2+. However, we found that there are metastable configurations of oligosaccharide, which can decrease the dehydration barrier of surface Mg2+ by about 0.7-1.1 kcal/mol. In these configurations, the molecule lies relatively flat on the surface and forms a bridge shape. The hydrophobic space near the surface created by the nonpolar -CH groups of the oligosaccharide in the bridge conformation is the reason for the observed reduction of dehydration barrier.