A vibrational study by means of UV-Raman and FTIR-ATR measurements has been performed on sulfobutyl ether β-cyclodextrin (SBE-β-CD)-water solutions, as a function of concentration and temperature, with the aim to provide a molecular-scale explanation of the enhanced performances as carrier agent exhibited by this modified macrocycle with respect to natural cyclodextrin. The attention has been mainly paid to the modifications induced on the vibrational band assigned to the O-H stretching intramolecular mode, in turn related to the dynamical rearrangement occurring in the hydrogen bonding (HB) network of water molecules. The results of our measurements clearly showed a characteristic "structure-breaker" effect on the tetrahedral HB arrangements induced on water molecules by increasing of both temperature and solute concentration, allowing us to also extract thermodynamic parameters. These results could be a key step for a clearer understanding of the connection between the dynamical properties of hydration water and the complexing ability of this cyclodextrin derivative.