The state of water in water-swollen poly(vinyl alcohol-co-itaconic acid) membranes, having various water contents from 0.31 to 0.83, was investigated by d.s.c. measurements and compared with those in water-swollen poly(vinyl alcohol) membranes. The amount of freezing water in the membranes was estimated by use of a relationship between the phase transition temperature and the enthalpy of the crystallization of supercooled water. The melting temperature of the water in the membranes immersed in urea and NaCl 0-2 mol l-1 aqueous solutions was also determined by d.s.c. analysis. The present study proposes a method for estimating the solubilities of urea and NaCl in both of the freezing and the non-freezing water using the melting point depression of the freezing water in the membranes immersed in the solute solution.