Self-stratification strategy can be used to prepare films in which both bulk and surface properties can be optimized. By using this approach, only a very small quantity of fluorinated species is needed to generate a surface with low surface energy. When cross-linking is involved during film formation, we are dealing with a competition behavior between the diffusion of fluorinated species and the formation of cross-linked network. In this study low surface energy polymeric films were prepared on the basis of partially fluorinated polyisocyanates, in combination with hydroxyl-end-capped three-armed solventless liquid oligoesters and modified hyperbranched polyesters. At a fluorine concentration of only 0.5 wt.%, contact angles of water and hexadecane can reach 120° and 80°, respectively. A surface energy as low as 10¿15 mN/m can be obtained upon the addition of less than 1 wt.% of fluorine in the films. It was shown, from real time ATR-FTIR and contact angle measurements, that the curing temperatures demonstrated significant effects on the cross-linking rate as well as on the wettability of the films.