Water sorption of coating materials is the main cause of coating deterioration, adhesion loss and substrate corrosion. By introducing alkanethiol self-assembled monolayers (SAMs), a hydrophobic interfacing layer between coating and substrate metal can be constructed. The effect of the hydrophobic SAMs interfacing layer on the corrosion protection of epoxy coatings was evaluated using electrochemical techniques including Tafel polarization, electrochemical impedance spectroscopy and impedance - time transition measurement. It was found that the SAMs interfacing layer improved the corrosion protection of the coating significantly. The improvement was attributed to the strong interaction between SAMs and the metal substrate, the compact structure and low water affinity of the SAMs interfacing layer, which prevent water absorbed by the coating from reaching the coating - metal interface and spreading along the interface.