The dehydration of prednisolone sesquihydrate is studied and characterized by different physico-chemical analysis methods. The meticulous study of this dehydration led to the highlighting of a new solid form (form 3), metastable, never identified before. In a second step, the rehydration of anhydrous forms 1 and 2 of prednisolone is studied, in particular by Dynamic Vapor Sorption. It is then demonstrated that neither of the two forms is sensitive to humidity. By means of solid-gas equilibria, the sesquihydrate can only be obtainable from the isomorphic anhydrous form. Finally, a classification of the sesquihydrate is made, taking into account, in particular, the activation energy determined during dehydration.
