A quaternized diol,3-(trimethylammonio)-1,2-propanediol neutralized with either bromine or iodine, was used to produce a polyurethane cationomer with a poly(tetramethylene oxide) soft segment and a 4,4’-diphenylmethane diisocyanate hard segment. If these cationomers were annealed at room temperature for a period of approximately 1 month in a desiccator filled with dry CaSO4, differential scanning calorimetry (DSC) studies showed an endotherm centered near 70-degrees-C which was not present in the unannealed polymer and did not reappear upon subsequent cooling and heating cycles in the DSC. Some authors have suggested that a very similar endotherm found in other ionomers, mostly notably ethylene-methacrylic acid (E-MAA) copolymer ionomers, was due to an order-disorder transition within the ionic aggregates, i.e. ionic crystallite melting. In order to isolate the origin of this endotherm, the local environment around the anion in compression molded bromine neutralized samples was measured using the extended X-ray absorption fine-structure (EXAFS) technique. By measuring the change in the local environment over the temperature range corresponding to the DSC endotherm, it has been shown that this endotherm corresponds to water leaving the bromine coordination shell, rather than ionic crystallite melting. Other studies which include thoroughly drying the material in a vacuum oven below the transition temperature to remove the water suggest that the endotherm is due to the energetic change associated with water leaving the coordination environment of the anion in combination with water vaporization.