The aim of the present work was to quantify accessible porosities for iodide and for a water tracer (HTO) on water-saturated compacted clay samples (illite, montmorillonite and MX-80 bentonite) and to relate these macroscopic values to the forms of water in these porosities (surface/bulk water, external/internal water). Low field proton NMR was used to characterize and quantify the forms of water. This enabled the three different populations (structural OH, external surface and internal surface water) to be differentiated on hydrated clays by considering the difference in proton mobility. An accurate description of the water forms within the different populations did not appear possible when water molecules of these populations were in contact because of the occurrence of rapid exchange reactions. For this reason, it was not possible to use the low resolution NMR method to quantify external surface and bulk water in fully water-saturated compacted clay media at room temperature. This latter information could however be estimated when analyzing the samples at -25°C. At this temperature, a distinction based on the difference in mobility could be made since surface water remained in a semi-liquid state whereas bulk water froze. In parallel, accessible porosities for anions and HTO were determined by an isotopic dilution method using capillaries to confine the materials. HTO was shown to probe the whole pore volume (i.e. the space made of surface and bulk water). When the surface water volume was mainly composed of interlayer water (case of montmorillonite and bentonite), iodide was shown to be located in the pore space made of bulk water. When the interlayer water was not present (case of illite), the results showed that iodide could access a small fraction of the surface water volume localized at the external surface of the clay particles.