A comparative investigation of trehalose, sucrose, and maltose in water solution has been performed using Raman scattering experiments and Molecular Dynamics simulations. From the analysis of the O-H stretching region in the [2500, 4000] cm-1 Raman spectral range, which includes for the first time the contribution of 'free' water, and the statistical distribution of water HB probabilities from MD simulations, this study confirms the privileged interaction of trehalose with water above a peculiar threshold weight concentration of about 30%. The role of the hydration number of sugars-found higher for trehalose-on the destructuring effect of the water hydrogen bond network is also addressed. The analysis of the water O-H-O bending spectral range [1500, 1800] cm-1 reveals a change of the homogeneity of water molecules influenced by sugars, but the three investigated sugars are found to behave similarly. © 2005 Elsevier Ltd. All rights reserved.