A combined NMR and TOF-SIMS study has been carried out on 1H,1H,2H-perfluorododecene plasma polymers. Pulsed plasma polymerization is found to give rise to a high level of structural retention for the perfluoroalkyl groups, whereas continuous wave condition., lead to monomer fragmentation and cross linking. This investigation provides unequivocal proof that pulsed plasma deposition is a simple and highly effective method for functionalising solid surfaces. (c) 2005 Elsevier Ltd. All rights reserved.