The synthesis of organic-functionalized pure-silica-zeolites (PSZs) with MFI- and MEL-type structures for low-k applications prepared through a direct-synthesis method by adding a fluorinated silane to the synthesis solution is reported. The added fluorine functionality increases the hydrophobicity of the zeolites, which are characterized by scanning electron microscopy, X-ray diffraction, Si-29 and F-19 solid-state NMR spectroscopy, nitrogen adsorption, and thermogravimetric analysis. The functionalized zeolite powders have low water content and calcined spin-on films prepared from the functionalized nanoparticle suspensions exhibit higher water contact angles and lower k values (2.1 and 1.8 for the functionalized MFI- and MEL-type zeolites, respectively) than PSZ films. The use of a direct-synthesis method to decrease the moisture adsorption in the films eliminates the extra post-spin-on silylation steps that are traditionally used to render the zeolite films hydrophobic.