The modelling of chloride transport in concrete under an electrical field requires taking into account the electrode processes. These processes are very rarely introduced into the literature, despite their impact on chloride migration and the electroneutrality of the pore solution of the material. This paper aims to propose a multi-ion model for chloride migration that takes into consideration the electrode processes. The model is applied to simulate the standard chloride migration test. The generation of OH− in the cathode and H+ in the anode allows for the monitoring of the electroneutrality. The model considers all of the ions in the pore solution. Ion fluxes are calculated using the Nernst–Planck equation. The Langmuir model is used to simulate the chloride isotherms. The thermodynamic equilibrium in the material is considered, which reflects the ion–solid interactions during the migration. Measurements of water porosity and the chemical composition of the pore solution are essential to provide input data and the initial and boundary conditions. The numerical results of the ion profiles in the material studied confirm the electroneutrality at any point within the material, in contrast with models that do not take the electrode processes into account. The proposed model allows for the more accurate simulation of the chloride migration test and electrochemical chloride extraction in reinforced concrete structures subjected to NaCl as part of maintenance and repair strategies.