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A quantitative analytical method for PFAS determination in airborne particulate matter (PM) has been developed using liquid chromatography coupled with high-resolution mass spectrometry (LC-HRMS), allowing for the determination of 33 compounds. The procedure was applied to ambient PM10 with limits of quantification for PFAS in the fg m−3 range. PM10 samples collected during a year-long campaign conducted in an urban site in Umbria (Central Italy) have been characterized for their PFAS content. Among the seven detected PFASs, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) were the most abundant compounds. Furthermore, this work allowed us to obtain the first seasonal trend of airborne PFASs in Central Italy. Seasonal trend analysis shows that PFAS concentration in the atmosphere peaks in summertime. A comparison with trends of other relevant primary and secondary air pollutants determined at the sampling site suggests a secondary nature of the observed PFAS, which are formed in the atmosphere directly from gaseous precursors and can contribute to worsen the urban air quality in summertime.