A hydrophobic benzoxazine-cured epoxy coating (EPB) was prepared by a dip coating and thermal curing method using benzoxazine monomer (B-TMOS) as curing agent. Fourier transform infrared (FTIR) analyses confirmed the presence of thermal curing reactions and hydrogen-bonding interactions in the epoxy/polybenzoxazine system. The hydrophobicity of epoxy coatings induced by the incorporation of B-TMOS was enhanced significantly, and the water contact angles of resultant EPB coatings were higher than 98°. The corrosion protection ability of epoxy coatings was investigated by open-circuit potentials, potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) methods. The results showed that the charge transfer resistance (R ct ) of EPB coatings was increased by about three orders of magnitude compared with bare mild steel, and the protection efficiency values of all EPB samples were more than 98%. This increased corrosion protection property could be attributed to the high hydrophobic performance of EPB coatings.