Abstract: A special integral form of the solution of Fick's law was applied to study the self-diffusion of Na, Cs, and Ca ions in Wyoming bentonite plugs by means of a radioactive tracer technique. A simple procedure for measuring diffusion coefficients was developed by depositing a thin radioactive tracer film on the surface of clay mineral plugs at controlled temperatures. Thin sections of the clay plugs were removed and radioactivity measurements made on the portion of the plugs remaining. The self-diffusion coefficients of the ions were evaluated by a graphical method from the solution of Fick's law at special boundary conditions. Under oven-dry conditions at 105°C diffusion of Na ion in a bentonite film was observed, while in the same experiment, SO 4 2− ion did not diffuse. In a clay-water system, however, the anion diffused much more rapidly than the cation. Based on the experimental results of observing Na22- and Sa35-tagged Na2SO4 diffusion, different diffusion paths were proposed using a picture of the clay matrix as a structure with “channels.” Diffusion coefficients of exchangeable cations decreased with increasing clay contents. From the results of activation energy and self-diffusion coefficients of Na and Ca ions at various clay-water concentrations, the relative “hopping distances” of diffusing ions were calculated and discussed. It is suggested that in the self-diffusion of exchangeable Na ion in bentonite the ion could be hopping from one individual clay plate to another, and the Ca ion from one “package” of plates to another “package” of plates.