This second part of the work deals firstly with carrying out materials characterization, mainly mercury intrusion porosimetry and chloride electrodiffusion tests on two cement pastes. Experimental data allowed fixing the perturbation parameter ϵ and other dimensionless numbers highlighted in part I of this work. Secondly, a series of parametric simulations were performed in order to compute the chloride diffusion coefficient through a gradual complexity of the elementary cell, approaching as close as possible the real microstructure of the cement pastes tested. Results highlighted that taking into account microstructure parameters (porosity, tortuosity and constrictivity) allows to approach the experimental diffusion coefficient. However, they also showed that electrochemical interactions between ions and the liquid-solid interface, and the multi-scale character of cementitious material microstructure, must be considered. Copyright © 2012 John Wiley & Sons, Ltd.