Using neutron reflectivity, the protection mechanisms of a novel one-step epoxy-silane coating system were investigated in terms of coating structure and water response behavior. By comparing pure epoxy and epoxy-silane mixtures in various aqueous environments, the effects of the addition of silane were determined. Specifically, a bridged bis-silane coupling agent with six alkoxy moieties and a polysulfur bridge was investigated. The key mechanisms of silane-enhanced protection are (1) the silane is enriched at the substrate-coating interface, forming a hydrophobic dense interfacial layer and good adhesion to the substrate, and (2) the silane serves as a cross-linker, resulting in a denser and less hydrophilic bulk film compared to the neat epoxy. The hydrophobic nature of bis-sulfur silane also increases the overall hydrophobicity of the mixed film.