In this study the erosion of poly(vinyl fluoride) Tedlar by hyperthermal atomic oxygen (AO) has been examined using X-ray photoelectron spectroscopy (XPS). Initially the Tedlar film had F/C and O/C atom ratios of 0.45 and 0.11, which decrease to 0.018 and 0.04, respectively, after a 2-h exposure to a flux of 2 x 10(15) atom s/cm(2) s AO with an average kinetic energy of 5 eV. This exposure essentially produced a graphitic or amorphous carbon-like layer with a carbon content greater than 90 at.%. Longer AO exposures do not alter the composition of this layer significantly. Exposure to O-2 or air nearly doubles the oxygen content in the near-surface region. This is due to dissociative oxygen adsorption at reactive sites formed at the polymer surface during AO exposure. Further exposure to AO removes this chemisorbed oxygen. (C) 2004 Elsevier B.V. All rights reserved.