A cylindrically configured plasma treatment system for Radio Frequency Glow discharges fed with ammonia was used to modify the internal surface of ePTFE arterial protheses to improve their biocompatibility. For a better understanding of the effects of this type of treatment oil the surface, RF-plasmas were also performed on PTFE films. The surface chemical composition was then characterized by XPS. The initial analyses showed that 15% of the surface atoms were replaced by nitrogen (N/C ratio of 0.3), whereas the F/C ratio decreased from 2 to 0.7-0.5 which indicates that the treated surfaces presented different chemical species, such as amine, imine, amide, acid groups, and insaturations. As XPS analyses could not lead directly to the nature of the N-species grafted on the surface (the chemical shifts being not significantly different), chemical derivatization was thus performed. Vapor phase chemical derivatization was carried out oil model polymers to evaluate the reactivity and the selectivity of each reagent toward each of the expected functional groups. The results indicate that benzaldehyde derivatives were good derivatizing reagents for amine groups, whereas bromine was the reagent of choice to quantify the insaturations. Using these methods, the amine and alkene concentrations on the surface were found to increase according to plasma treatment time rising from their initial value of 3% for a 50 s plasma treatment to 6% for a 250 s plasma treatment. AFM studies on oriented Teflon films also demonstrated that the Occurrence of chain breaking increased with plasma treatment time. It therefore appears that determining the treatment parameters should require the best compromise between several effects such as nitrogen grafting, amine and alkene formation, and chain breaking.