Plasma-deposited thin films of fluoropolymer on metallic substrates were degraded by low-energy (1–100 eV) electrons and X-ray irradiation to simulate irradiation conditions of implanted coated stents in the human body during diagnostic procedures using high energy radiation. The desorption of anions and cations from the surface of the films induced by 1–100 eV electrons was recorded by mass spectrometry. The electron energy dependence of the emission of F− exhibited a resonant peak at 12.9 ± 0.4 eV, showing the formation of a transient excited anion and a monotonic rise at higher energies, associated to dipolar dissociation. In the positive ion mode, the fragments F+, CF+, CF2+, CF3+, C3F3+, C2F4+ and C2F5+ were observed. Emission thresholds were measured and laid above 25 eV. The shape of the cation emission curves versus electron energy showed no resonant process. X-ray degradation was studied by X-ray photoelectron spectroscopy for different exposure times. Loss of fluorine in –CF2 groups was observed and damage mechanisms were proposed.