A new method for the formation of tightly bound, low-surface-energy nanocomposite coatings on glass and other hydroxylated surfaces is reported. This technique involves the initial deposition of a porous vanadia-silica sol-gel thin film on the surface of the substrate. These coatings act as reactive interfaces for the photopolymerization of vinyl monomers, Using this interface, polyvinylidene fluoride (PVF2)-silica nanocomposite coatings on quartz were fabricated. These coatings were found to be extremely robust and yielded a surface whose energy was close to that of pure PVF2.