Neutral, volatile polyfluorinated alkyl substances (PFAS) were measured in environmental air samples at two different sites in Northern Germany in spring 2005. The sampling locations were chosen to cover a metropolitan and a rural site, the Hamburg city center, and Waldhof, a background monitoring site. An optimized and validated analytical protocol was used to analyze two sets of parallel high-volume air samples. For both sampling locations as well as for individual samples, field blanks were taken to monitor possible background contamination. Gas chromatography coupled to mass spectrometry using positive chemical ionization (GC/ PCI-MS) was used for quantitative analyses. This article describes the first air concentration data of volatile PFAS outside North America reported in the peer-reviewed literature. The wide distribution of fluorotelomer alcohols (FTOHs), fluorinated sulfonamides, and sulfonamidoethanols (FOSAs/FOSEs) in German environmental air is presented. Furthermore, two volatile PFAS, i.e., N-methyl fluorooctane sulfonamide (NMeFOSA) and 4:2 FTOH, were determined for the first time in environmental air. Minimum-maximum ΣFTOH concentrations of 64-311 pg/m ³ (remote) up to 150-546 pg/m ³ (urban) and minimum-maximum ΣFOSA + FOSE concentrations between 12 and 54 pg/m ³ (remote) and 29 and 151 pg/m ³ (urban) were determined. 8:2 FTOH and 6:2 FTOH were found to be the predominant POPs determined in Waldhof so far. Blank contamination was found to be negligible. A significant correlation was found with the ambient temperature for the partitioning of airborne FOSEs between the gaseous and particulate phase (R = 0.853), whereas FTOHs and FOSAs were almost exclusively found in the gaseous phase. Furthermore, highest airborne PFAS concentrations were determined at relatively high ambient temperatures. Correlation coefficients (R) for ΣFTOH and ΣFOSA + FOSE concentrations with temperature were 0.954 and 0.968, respectively. Finally, the PFAS concentrations determined in this study are set into context with levels of "classical" persistent organic pollutants (POPs) in the same region and PFAS data available for North America.