Organically functionalized mesoporous silica films have been prepared by a novel synthetic procedure that involves spin-coating of mesostructured silica films and a vapor infiltration (VI) technique, using organosiloxanes, before the removal of surfactant. The VI-treated mesostructured films were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and a field emission scanning electron microscope (FE-SEM). Nitrogen adsorption/desorption measurements were performed using films attached with a silicon substrate. The XRD and FE-SEM measurements show that the mesochannel wall, densified and modified with organosilyl groups by the VI treatment, hardly contracts under calcination. FE-SEM observations for the films' cross section support the view that organosiloxane vapor is not deposited on the surface of the film. These results show that organosiloxane molecules penetrate the film and are selectively incorporated into the silica wall. Thus, hydrophobic mesoporous silica films can be synthesized without a reduction in pore size, a result that cannot be attained by conventional grafting and co-condensation methods. The excellent high porosity and hydrophobicity of the mesostructured composite films may be of advantage for next-generation low-k dielectric films.