In this first part of the work, we develop macroscopic models for migration and diffusion–migration of ionic species in saturated porous media, based on periodic homogenization. The prior application is chloride transport in cementitious materials. The dimensional analysis of Nernst–Planck equation lets appear to dimensionless numbers characterizing the ionic transfer in the porous medium. Using experimental data obtained from electrodiffusion tests on cement-based materials (Part II), these dimensionless numbers are linked to the perturbation parameter ϵ. For a strong imposed electrical field, the asymptotic expansion of Nernst–Planck equation leads to a macroscopic model where the migration is predominant. For a weak imposed electrical field or in natural diffusion, we obtain a macroscopic model coupling diffusion and migration at the same order. In both models, the expression of the homogenized diffusion tensor is identical and only involves the geometric properties of the material microstructure. Copyright © 2012 John Wiley & Sons, Ltd.