A method intercomparison study of analytical methods for the determination of neutral, volatile polyfluorinated alkyl substances (PFAS) was carried out in March, 2006. Environmental air samples were collected in triplicate at the European background site Mace Head on the west coast of Ireland, a site dominated by ‘clean’ westerly winds coming across the Atlantic. Extraction and analysis were performed at two laboratories active in PFAS research using their in-house methods. Airborne polyfluorinated telomer alcohols (FTOHs), fluorooctane sulfonamides and sulfonamidoethanols (FOSAs/FOSEs) as well as additional polyfluorinated compounds were investigated. Different native and isotope-labelled internal standards (IS) were applied at various steps in the analytical procedure to evaluate the different quantification strategies. Field blanks revealed no major blank problems. European background concentrations observed at Mace Head were found to be in a similar range to Arctic data reported in the literature. Due to trace-levels at the remote site, only FTOH data sets were complete and could therefore be compared between the laboratories. Additionally, FOSEs could partly be included. Data comparison revealed that despite the challenges inherent in analysis of airborne PFAS and the low concentrations, all methods applied in this study obtained similar results. However, application of isotope-labelled IS early in the analytical procedure leads to more precise results and is therefore recommended.