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Fluorinated coatings of solid surfaces are important for many applications ranging from corrosion resistance to low surface energy biological interfaces. We present a facile approach to coat solid-state surfaces directly from vapor phase without harsh chemical or plasma treatments. The coatings show nanostructures with high surface area, which is important for variety of surface functionalizations, for example, in molecule attachment and cell growth. The novel polymeric nanoporous film is achieved from the reaction and deposition of two molecules. The surface morphology and pore sizes of the coating on solid-state surfaces can be tuned with change in concentration of monomers in a simple reaction chamber. The X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy analyses show organic nature of the coating. Cell growth studies are done to gauge biocompatibility and adsorption of proteins and cells. The approach can be used to coat, functionalize, and treat nano- and microstructures for a variety of applications with minimal chemical footprint.