This work documents the modeling of ionic transfer through porous materials under an external electrical field. A pore model network that accounts for the electrical double layer impact was developed and scaled up at the porous material level. The model is adapted to two different materials, both belonging to the class of mesoporous materials: a monomodal porous glass, and a cement paste with mineral additions. The comparison between numerical results and experiments on migration and tritium natural diffusion questions the concept of formation factor applied to such mesoporous materials.