The fundamental features and industrial applications of the direct fluorination of polymers are reviewed. Direct fluorination of polymers (i.e., treatment of a polymer surface with gaseous fluorine mixtures) proceeds spontaneously at room temperature and is a surface modification process. More than 25 polymers have been studied with the aid of a variety of analytical and spectroscopic techniques. The fundamental features of the direct fluorination, such as influence of treatment conditions (composition of the fluorinating mixture, fluorine partial pressure, temperature, and fluorination duration) on the rate of formation, chemical composition, density, refraction index, and surface energy of the fluorinated layer, kinetics of formation of radicals during fluorination and their termination, texture of fluorinated layer, etc. were studied. It was demonstrated experimentally that direct fluorination can be effectively used to enhance commercial properties of polymer articles, such as barrier properties of polymer vessels, bottles, and packaging films and envelopes; gas-separation properties of polymer membranes; adhesion and printability properties of polymer articles; and mechanical properties of polymer-based composites.