The corrosion behavior of a pure aluminum/pure magnesium couple in a weakly conductive sodium sulfate solution was investigated. Potential and current distributions on the surface of the model couple at the beginning of immersion were obtained by solving the Laplace equation using a finite element method algorithm. Magnesium acted as the anode of the system while oxygen and water were reduced on aluminum. Calculations predicted a large current peak at the Al/Mg interface related to a local increase in both Mg dissolution and oxygen and water reduction on aluminum, leading to a local pH increase. Optical and scanning electron microscope observations confirmed the strong dissolution of magnesium concomitantly with depassivation of aluminum at the Al/Mg interface. Local electrochemical impedance spectroscopy showed the detrimental effects of the galvanic coupling both on aluminum and magnesium.