Molar enthalpies of solution at very low molalities of some mono-, di, tri, and tetra-saccharides in water have been measured at 298.15 and 308.15 K using an isoperibol calorimeter. The molar heat-capacity changes Δ sol C p , m ∞ on dissolution at 303.15 K were derived from molar enthalpies of solution. A Picker flow microcalorimeter and an Anton Paar digital density meter were used to measure apparent molar heat capacities C p, 2, φ and apparent molar volumes V 2, φ of solute at 298.15 K. The various compounds studied show large positive values of Δ sol C p, m ∞ and C p, 2 ∞. The experimental C p, 2 ∞ values are found to be much higher than values estimated using additivity relations and heat capacities for the constituent groups derived from the heat capacities of monofunctional compounds. Results further indicate that the difference in C p, 2 ∞(expt) and C p, 2 ∞(est.) per hydroxyl group increases with an increase in the number of hydroxyl groups in a molecule. An attempt has been made to explain the C p, 2 ∞ values of stereoisomers in terms of the compatibility of the aqueous-solution conformation of the compound and the tetrahedral order in water.