Raman measurements at room temperature reveal a characteristic concentration for a series of aqueous solutions of electrolytes, through which O–H stretching vibration of H2O or dilute HDO obviously changes their concentration depen-dence. This characteristic concentration is very consistent with another, through which the solutions undergo an abrupt change in their glass-forming ability. Interestingly, the molar ratio of water to solute at these two consistent concentration points is almost solute-type independent and about twice the hydration number of solutes. We suggest that just when the concentration increases above this characteristic concentration, bulk-like free water disappears in aqueous solutions and all water molecules among closely-packed hydrated solutes exhibit the characteristics of confined water.