In this article, highly-hydrophobic polyurethane coatings with low limiting wetting angle hysteresis were received by the surface modification with sol-gel technology. The influence of sol components on structure of obtained gels in acid- and base-catalyzed sol-gel process examined by both Fourier-infrared and nuclear magnetic resonance spectroscopy. Influence of tetraethoxysilane and 3-aminopropyltriethoxysilane ratio on wetting of xerogels coating was shown. Particle size distribution in receiving sols was investigated. By atomic-force microscopy and scanning electron microscopy the topography and the morphology of the surface of polyurethane coatings modified by xerogels were studied