In this paper, an example of the application of the homogenization approach (asymptotic expansion technique) to predict the effective diffusion coefficient for an equivalent continuum, together with the experimental verification of the theoretical results is presented. The experimental setup was constructed for the measurements of diffusion in a model periodic porous medium made of Plexiglas. The computer program using the FEM was elaborated to solve the local boundary value problem for a period and to calculate the effective diffusion coefficient. The comparison between the theory and the experiment indicates good agreement between the numerical and experimental values of the effective diffusion coefficient. Interpretation of the test data from the point of view of the homogenization theory is also incorporated.