This review focuses on the thermal properties of bound water restrained by various kinds of polysaccharides and several synthetic polymers. The characteristic features of freezing bound water which is closely related with biocompatibility of polymers are summarized based on results obtained by differential scanning calorimetry. Glass transition, cold crystallization and melting of water-polysaccharide systems were observed. Three kinds of water, non-freezing, freezing bound and free water, were quantified from the enthalpy of melting of water in the system. Freezing bound water restrained by polysaccharides is in a metastable state. The equilibrium melting temperature of freezing bound water is lower than 0°C and the temperature decreases with decreasing water content. Nucleation and growth rate of freezing bound water were calculated from isothermal crystallization and the values were compared with those of free water.