In this work we present non-destructive measurements of sodium ion concentration profiles during the electrokinetic removal of sodium chloride from porous materials using Nuclear Magnetic Resonance (NMR). The effect of both protons and hydroxyl ions, generated due to the electrolysis of water, on the transport of the salt ions is studied by tracking the acidic and alkaline fronts using pH-indicator paper. In addition, the electrical potential distribution within the specimen is monitored to assess its influence on the process. To support the observations we compare the experimental results with a theoretical model based on the Poisson–Nernst–Plank equations. In this model we use the chemical equilibrium condition for the self-electrolysis of water in the description of the transport of protons and hydroxyl ions. In addition we use the electro-neutrality condition to compute the transport of salt ions through the material. At the edges of the system the electrical current is distributed over the chemical active species, i.e. protons, hydroxyl and chloride ions, according to the Butler–Volmer description for charge transfer at electrodes. Both the experimental and model results show in the final stage of the electrokinetic remediation process a sharp transition from the acidic to alkaline region at one third of the length of the specimen away from the positively biased electrode, i.e. the anode. From the model results we found that the formation of chlorine gas at the anode does not influence the position of this transition area. In this transition region we also observe a large gradient in electrical potential and a corresponding local deficit of ions. As a result of the large potential gradient in this small transition zone the electrical field in the acidic and alkaline region diminishes. Consequently, electrokinetic ion transport though the material will stagnate.