In this contribution, a new method is proposed for determining effective macropore diffusion coefficients in porous media by digitized microphotographs of porous support materials and random walk simulations. The method introduced allows calculation of the effective diffusion coefficient as a function of the mean free path length over a wide variety of values. A versatile method for the preparation of porous substances for light microscopy is described. The frequently applied model of an active shell, which is used to model particle/solid collisions, was found to give incorrect results in conjunction with the application of the first passage time algorithm, which was applied to save computing time in the simulation of gas diffusion. It was possible to show that more realistic results are obtained if a Knudsen layer is used to model particle/solid collisions. Furthermore, in investigating diffusion in two- and three-dimensional representations of capillary tubes, it was found that results of simulations performed to calculate transport properties of fluids in porous media, based on two-dimensional model systems, cannot in any case be transferred to the corresponding three-dimensional systems.