A thermal analysis of the effect of hydration of non-aqueous polymer-stabilised gels was investigated using differential scanning calorimetry (DSC). The interaction of water with the polymer and its distribution within the gel are critical to the physicochemical behaviour of the gel, and consequently affects the utility of the gel matrix as a drug delivery vehicle. Addition of water at levels up to and including 50% (w/w) did not result in an observable freezing event in the thermogram. However, at 60 and 80% (w/w) water, phase transitions were observed, the magnitude of which were found to be independent of the annealing time within the range used. The observed melting enthalpies increased as the water concentration increased for all formulations, but were always smaller than that of pure water. There was no evidence of multiple transitions that might be attributed to different populations of water molecules. However, the results demonstrate that DSC can be employed to differentiate between freezable and non-freezable water, in these particular formulations. (C) 2004 Elsevier B.V. All rights reserved.