Triethoxysilane groups were covalently attached onto the surface of ethylene-vinyl alcohol (EVOH) copolymer film via a urethane linkage through reaction between the hydroxyl groups in EVOH and 3-isocyanatopropyltriethoxysilane in the presence of dibutyltin dilaurate as catalyst. This reaction was confirmed by ATR-IR and XPS analysis. XPS results also indicated that this reaction was not surface sensitive and the modified layer was at least 40 Angstrom in depth. The modified film samples were further reacted with tetramethoxysilane (TMOS) for partial hydrolysis and condensation and XPS results showed a significant increase in the contents of oxygen and silicone on the surface which confirmed the above reaction.