In this study the chemical alteration of poly(vinyl fluoride) Tedlar (R) by vacuum ultraviolet radiation (VUV) (115-400 nm) has been examined using X-ray photoelectron spectroscopy (XPS). The initial F/C atom ratio of 0.34 decreases to 0.17 after a 2-h exposure. The F/C atom ratio is further reduced to a steady-state value of approximately 0.04 after a 24-h exposure. Similarly, the O/C atom ratio is reduced from 0.08 to 0.05 and then to 0.02 during these two exposures. As the F and O are removed by VUV exposure, the C concentration increases from 70.5 to 82.0 and then to 94.6 at.% thus forming a graphitic or amorphous carbon-like layer which erodes more slowly than the virgin Tedlar Surface. Exposure of the VUV-damaged surface to O-2 results in chemisorption of O, indicating that reactive sites are formed during the chemical erosion by VUV. Further exposure to VUV removes this chemisorbed oxygen but a subsequent exposure to air at atmospheric conditions causes a three-fold increase in O chemisorbed at the surface. Comparison of XPS data indicates that the mechanisms of chemical alteration by VUV radiation and hyperthermal (similar to 5 eV) atomic oxygen (AO) are similar. (c) 2005 Elsevier B.V. All rights reserved.