Graphene nanomaterials improve electrical and thermal conductivity in coatings and enhance barrier properties against diffusive molecular species. Using a two-step process, a superhydrophobic coating with highly effective anti-corrosion properties was obtained using a thiol-ene UV curable thermosetting resin incorporating silica nanoparticles (Si-NP) and graphene oxide (GO). The Si-NP offers a dual-scale roughness structure which leads to superhydrophobicity based on the Cassie-Baxter wetting principle. The GO is a barrier layer for diffusion, dramatically enhancing corrosion resistance efficiency. It also mediates the electron-transfer process between the corrodent environment and the carbon steel substrate. A superhydrophobic property with a highly crosslinked structure offers excellent chemical resistance and adhesion strength promising high environmental durability as coatings.