The work aims to study and develop a kind of polyvinyl alcohol (PVA) film material with single-sided hy-drophobic property as packaging material. PVA-SiO2 films were prepared by tape-casting drying with 12% (mass fraction) PVA solution with 88% alcoholysis degree and 5% (mass fraction) nano-SiO2 solution heated and stirred at 1:1 volume ratio. Then, one side of the film was modified by 2.5%, 5% and 7.5% heptafluorodecyl trimethoxysilane (FAS)-ethanol solution, and the modified results were characterized by solubility test, contact angle test, field emission scanning electron microscopy (FE-SEM) and Fourier transform attenuated total reflection infrared spectroscopy (ATR-FTIR). The results indicated that, the one-sided hydrophobicity of the films was improved. The dissolution time of modified film in water increased and the contact angles of all kinds of modified films were above 120°, which meant that FAS did play a role in lowering the surface energy. FE-SEM results showed that, the content of Si element had an important influence on the hydrophobicity of the films. ATR-FTIR showed that, fluorine atoms were successfully introduced into the film surface after FAS modification, and the number of silicon atoms was increased. The hydrophobicity of the film modified by 5% (mass fraction) FAS-ethanol solution was the best, and the contact angle reached 126.21°. The hydrophobic properties of PVA-SiO2 films after single-sided modification by FAS are much better than those of unmodified ones, which widen the application field of PVA film materials.