The wide growth in the nuclear activities results in an increasing subsequent influx of radioactive wastes into the environment. This problem has manifested a great deal of interest aiming at finding out ways through which those wastes can be harmlessly isolated from the human environment. Geological disposal is considered as one of the most promising solutions that ensures a safe storage of radioactive wastes as long as their activities are above the accepted levels. Clay minerals are proposed as backfill buffering materials in the geological repositories that can delay the migration of the radionuclides through sorption and thus decrease the contamination of underground waters. The extent of retardation of the radionuclide migration is dependent on factors like time of contact, pH and Eh of groundwater, concentration, temperature and grain size of the mineral particles. In this study radiochemical, spectroscopic (ToF-SIMS, XPS), and X-ray diffraction techniques were applied to examine different aspects of the sorption behavior of cesium, barium and cobalt on three natural clay minerals containing primarily kaolinite, illite-chlorite, and bentonite. The elements cesium (Z=55), barium (Z=56), and cobalt (Z=27) have the radioactive isotopes superscript 137 Cs (half-life=30.17 years), superscript 140 Ba (half-life=12.79 days), and superscript 60 Co (half-life=5.3 y) which are important in radioactive waste management. The first two radionuclides are produced in high yields in nuclear fission, whereas the third is an activation product. The natural clay samples that were used in this study originated from natural mineralogical beds at Sindırgı, Afyon, and Giresun regions in Turkey. The characterization of these clay samples showed that the primary clay minerals were kaolinite in Sındırgı clay, chlorite and illite in Afyon clay, and montmorillonite in Giresun clay. Each of these clays possesses different structural properties that result in different sorption capabilities. Radiochemical batch experiments were carried out to examine the effects of time, concentration, and temperature on the sorption of cesium, barium and cobalt on clays. Solutions of these cations spiked with several microliters of the radionuclides 137 CS (half-life=30.1 y), 133 Ba (half-life=10.7 y), and 60 Co (half-life=5.3 y) were monitored using gamma-ray spectroscopy prior to and after each sorption experiment. These results showed that equilibrium is achieved within two days in all cases. The sorption data was adequately described by Freundlich and Dubinin-Radushkevich isotherm models. Based on the parameters of those isotherm models, it was found that sorption was nonlinear, and that bentonite showed the highest sorption affinity and sorption capacity towards the sorbed ions. The thermodynamic parameters indicated that while sorption of cesium and barium on the three clays is exothermic that of cobalt is endothermic. The obtained values of Gibbs free energy change, Delta G degrees, were generally in the 8-16 (kJ/mol) energy range that corresponds to ion exchange type sorption mechanism. Since sorption is mainly a surface phenomenon, part of our sorption studies were carried out using the surface sensitive techniques; Time of Flight- Secondary Ion Mass Spectroscopy (ToF-SIMS) and X-ray Photoelectron Spectroscopy (XPS). In addition, depth profiling up to 70 angstroms was performed using ToF-SIMS to investigate cesium, barium and cobalt concentrations through the clay surface. ToF-SIMS and XPS studies were helpful in figuring out the surface composition of different clays prior to and after sorption. Quantification of the depletion of different alkali and alkaline-earth metals initially contained within the analyzed clay surface showed that ion exchange plays a primary role in the sorption process. In addition, X-Ray Diffraction (XRD) technique was applied to figure out the mineralogical composition of the clay minerals used and examine any structural change a accompanying the sorption process. XRD spectra of the clay samples after sorption showed that -apart from some intensity reductions in some clay features-, no primary changes were detected in the sorption cases of cesium and cobalt. In barium sorption, however, features belonging to barium carbonate were present in the spectra corresponding to sorption on chlorite-illite and bentonite.