Solid-solid transformations between solvates of pharmaceutical compounds are investigated under various conditions. In the case of Roxithromycin, it is shown that starting from single crystals of the acetonitrile solvate, a transformation towards the monohydrate occurs according to a cooperative mechanism. This smooth exchange of solvent probably involves a transport of matter within channels, and the comparison of crystal structures is consistent with the persistence of the main features of the 3D lattice. By contrast, starting from the DMSO solvate of Dexamethasone acetate, the transformation towards the sesquihydrated form, induced by the immersion of the DMSO solvate in water, is fully destructive and reconstructive. This occurs far-from-equilibrium and is therefore controlled by kinetic factors. The existence of an intermediate liquid phase within the particle is postulated to account for the appearance of whisker-like crystals growing first on high-energy sites of the former particle. An extended analysis of these transformations between solvates shows that they could be classified according to rules previously proposed in the case of desolvation mechanisms.