Composite materials are the most variative type of materials employed in almost every task imaginable. In the present study, a synthesis of a novel perfluoroalkyltriethoxysilane is reported to be used in creating composites with polyhexafluoropropylene—one of the most indifferent and adhesion-lacking polymers existing. The mechanism of adhesion of hexafluoropropylene is proved to be due to chemical structural coherence of perfluoroalkyltriethoxysilane to a link of polyhexafluoropropylene chain. The ability of perfluoroalkyltriethoxysilane to attach to surfaces was studied by FT-IR spectroscopy of modified glass microspheres. Although the perfluoroalkyltriethoxysilane surface modifier allowed partial adhesion of polyhexafluoropropylene, some detachment took place; therefore, the surface nanostructuring was used to increase its specific area by aluminum foil anodizing. An anodized aluminum surface was studied by scanning electron microscopy. The resulting composite consisting of anodized aluminum, perfluoroalkyl surface modifier, and polyhexafluoropropylene layer was proved to be stable, showed no signs of detachment, and is a promising material for usage in harsh environments.