Two different methods of surface modification of cotton fabrics are compared: direct fluorination using elemental fluorine and admicellar polymerization, which uses a surfactant and fluoromonomer system. Sample characterization includes infrared spectroscopy, analysis of mechanical properties, analysis of wetting times, contact angle measurements, scanning electron microscopy, elemental analysis, and atomic force microscopy analysis. Fourier transform infrared spectroscopy and elemental analysis showed the presence of fluorine moieties. For direct fluorinated cotton fabric, the static contact angle was found to be 117°, and for cotton fabric modified by admicellar polymerization, the contact angle was 125°. In all cases, the presence of a very thin fluorocarbon layer on the surface was confirmed, but differences in terms of the amount of fluorochemical formed and in surface structure were also found.