The corrosion protection mechanism of a one-step silane-laced epoxy coating system was investigated using neutron reflectivity. Pure epoxy and silane-laced epoxy films were examined at equilibrium with saturated NaCl water solution. The results demonstrate that the addition of silane introduces a salt-exclusion effect to epoxy coating. Specifically, the addition of silane densifies the epoxy network, which leads to exclusion of hydrated salt ions by a size effect. The effect is particularly significant at the metal-coating interface. Exclusion of ions improves the corrosion resistance, particularly for metals susceptible to pitting.