The vibrational (IR and Raman) spectrum of Vandenbrandeite, Cu[UO2(OH)(4)], has been recorded and discussed on the basis of structural considerations through the use of empirical expressions. As the H-bonding in the lattice is poorly known, the characteristics of this bond has been analyzed with the aid of H/D isotope exchange, thermal assays and electron microscopy. Samples are practically amorphous to XRD up to similar to 700 degreesC whereas crystals morphologically different by SEM microscopy and well characterized by XRD technique are observed from similar to 800 degreesC. Vibrational spectroscopy reveals that the atomic arrangement in the structure remains largely unaffected as the dehydration proceeds, suggesting a topochemically controlled process. EPR spectroscopy suggests a disordered distribution of Cu(II) ions as temperature increases. Finally, thermal dehydroxylation and paragenesis of the copper-uranyl oxide hydrate are correlated.