We describe a simple photochemical process which allows fluoropolymers to be chemically bound at room temperature onto SiO2 surfaces. To achieve this, at first a benzophenone silane is used to form a self-assembled monolayer on the surface of the substrate, which is subsequently coated with the fluoropolymer and irradiated with UV light of wavelength 365 nm. Using this very simple approach, we have been able to create ultrahydrophobic surfaces with very low surface free energies together with a good degree of control in thickness and composition as well as strong adhesion to the monolayer. The use of a UV-based process to attach the films on SiO2 surfaces opens the door for photopatterning of surfaces with fluorinated and nonfluorinated compounds to yield well-defined microstructures with spatial control of the wetting properties of the substrates.