A clayey soil from southern Tunisia has been studied in order to assess its possible use as an anti-pollution barrier. The soil has been characterized from both geotechnical and physicochemical points of view. The physicochemical characterization was carried out using X-ray diffraction, thermogravimetric and differential thermal analyses, specific surface area and cation exchange capacity measurements. Hydration tests were carried out using oedometers to determine the swelling behaviour of compacted specimens under different stress conditions. The large swelling pressure (420 kPa) is in agreement with the mainly smectitic character of the soil highlighted by the physicochemical tests. The changes in the fabric of the soil and in its porosity after the hydration tests were investigated using the same physicochemical methods, and related to the macroscopic hydro-mechanical properties. X-ray diffraction and mercury intrusion measurements show that there are changes in the interlayer spacing, particle size and inter-aggregate pore distribution. Comparing the properties of the soil with the Belgian guidelines for the construction of anti-pollution barriers showed that the material was suitable for that use.