The insertion of H2O in AlPO4-54 center dot xH(2)O at high pressure was investigated by single-crystal X-ray diffraction and Monte Carlo molecular simulation. H2O molecules are concentrated, in particular, near the pore walls. Upon insertion, the additional water is highly disordered. Insertion of H2O (superhydration) is found to impede pore collapse in the material, thereby strongly modifying its mechanical behavior. However, instead of stabilizing the structure with respect to amorphization, the results provide evidence for the early stages of chemical bond formation between H2O molecules and tetrahedrally coordinated aluminum, which is at the origin of the amorphization/reaction process.