The oxide layer and ternary eutectic of Zn–6Al–3Mg alloy coating have an important effect on its corrosion behavior and corrosion resistance, but the influence of oxide layer on the corrosion behavior of the coating and the internal corrosion mechanism of ternary eutectic structure are still unclear. In this study, the oxide layer and ternary eutectic of the coating were characterized in detail, and the corrosion behavior of the oxide layer and ternary eutectic in the environment containing Cl were studied based on first principles of density functional theory. The results show that the surface oxide layer can initially prevent the erosion of Cl-, MgZn2 in ternary eutectic preferentially corrodes after the oxide layer dissolves, corrosion products are formed.