Xenon difluoride (XeF2) plasma treatment of a series of polymers containing different repeat units gives rise to varying levels of surface fluorination. Alkene and aromatic C-H bonds appear to be more susceptible towards reaction compared to their sp(3) counterparts. The extent of fluorine incorporation can be accounted for in terms of a structure-behaviour relationship derived from extended Huckel molecular orbital calculations. Comparison with CF4 plasma modification shows that XeF2 electrical discharges are more effective at fluorinating polymer surfaces. (C) 2011 Elsevier Ltd. All rights reserved.