Water is often the main cause of adhesion loss of a polymer coating/substrate system. The buildup of the interfacial water layer and the loss of adhesion of polymer-coated siliceous substrates exposed to liquid water has been investigated. The thickness of the interfacial water layer was measured on epoxy-coated SiO2-Si prisms using FTIR-multiple internal reflection (FTIR-MIR) spectroscopy. Adhesion loss on flat siliceous substrates was determined by a wet peel test on epoxy-coated SiO2-Si wafers and adhesion loss of composites was obtained by measuring the interlaminar shear strengths of epoxy/E-glass fiber composites. Both untreated and 0.1 % silane-treated substrates were used. Little water was observed at the interface of the silanetreated samples but about 10 monolayers of water have accumulated at the interface of the untreated samples after 100 h of exposure to 24°C water. Untreated, flat substrates lost most of their bonding strengths within 75 h of exposure but silane-treated specimens retained 80% of their adhesion after 600 h of exposure to 24°C water. Adhesion loss of untreated composites immersed in 60°C water was greater than that of treated samples; however, the rate of loss of both silanetreated and untreated composites was much lower than that of flat substrates. Adhesion loss was found to follow the same trend as interfacial water buildup.