The use of clay materials as selective sorbents for different contaminants requires very efficient methods. A natural kaolinite was calcined to metakaolinite and than rehydrated at different temperatures to produce a highly porous sorbent. The kinetics of this process were measured, with subsequent IR characterization of the phases formed. The surface and pore distribution of new phases were also assigned. In addition, the kaolinite obtained was pre-treated with Fe3+ ions to improve its sorption affinity for anionic particles. The rehydrated kaolinite and its Fe-modification were used for the adsorption of toxic cations (Zn, Cd, Pb) and anions (As, Se). Adsorption capacities depending on the physical chemical properties of the initial solution (pH, concentration of toxic ions) and the surface properties of the sorbent (specific surface area, modification method) were investigated. The adsorption properties of the sorbents were defined by the Langmuir model.