The electrochemical technique for chloride extraction (desalination) was applied in galvanostatic mode to cylindrical brick and concrete specimens with a steel bar as reinforcement placed in the centre. The specimens were initially contaminated by immersion in a solution of 35 g/l NaCl. Based on the Nernst–Planck equations, a numerical model was developed considering the interactions between the various ionic species in the pore solution. The model makes it possible to predict the evolution of the chloride profile with time. The numerical and experimental results are compared and the model parameters discussed.