Simultaneous Differential Thermal Analysis/Thermogravimetric experiments carried out on one large single crystal, several small single crystals and powdered crystals of pentahydrate copper sulphate have been used to demonstrate the role that retained liquid water plays in maintaining crystal morphology during dehydration. Measured activation energies for stepwise dehydration in the system show the presence of solution-based transformations provide lower energy paths for the dehydration steps and stress relieving mechanisms. Skeletal anhydrous crystals from large-sized pentahydrate copper sulphate have the same morphology as the starting crystal on complete dehydration at controlled heating rates as long as a solution phase is maintained within the crystal during decomposition. The athermal activation energies, in this work, are in agreement with those obtained by isothermal methods as long as coincident reaction paths for the two techniques are maintained. The literature has been reviewed in the light of this work and a three-stage process is presented to rationalise the conflicting information obtained by workers using a variety of different experimental techniques.