Placed in a geological repository, radioactive bituminized waste (BW) could be altered in the long term by water, leading to the release of chemical and radioactive elements. The main difficulty, in terms of experimental characterization, comes from the fact that the BW material evolves in time due to the swelling associated to the water osmotic flux. To overcome this difficulty, a new approach is proposed in this work, based on the leaching of BW samples in aqueous solutions where the chemical activity of water is controlled. These specific leaching conditions allow one to control the swelling of the degraded BW matrix. The chemical activity of water being fixed, the pore structure of the leached BW samples was quantitatively studied by ESEM pictures further treated by image analysis. In parallel, diffusion cells using radioactive tracers were used in order to measure mass transfer characteristics in the leached BW. Coupling image analysis with diffusion experiments for each degradation state leads to a diffusion coefficient-porosity relation that is then compared to standard diffusion models in biphasic materials.