In order to determine the radionuclides' sorption constants on solid natural minerals, both thermodynamic and structural investigations, using spectroscopic techniques, are presented. The natural clays, that could be used as engineering barriers in the nuclear waste geological repository, are rather complex minerals. Therefore, in order to understand how these natural materials retain the radionuclides, it is necessary first to perform these studies on simple substrates such as single crystal, oxides and silicates, and then extrapolate the obtained results on the natural minerals. We examine in this paper the sorption processes of the hexavalent uranium on zircon (ZrSiO4) and the trivalent curium on a natural clay (bentonite). The corresponding sorption curves are simulated using the results obtained with the following spectroscopic techniques: laser induced spectrofluorimetry, X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (EXAFS), diffuse reflectance infrared Fourier transform (DRIFT). (C) 2002 Academie des sciences/Editions scientifiques et medicales Elsevier SAS.