Perfluoroalkyl acids (PFAAs) are a form of toxic pollutant that can be transported across the globe and accumulated in the bodies of wildlife and humans. A nationwide geographical investigation considering atmospheric PFAAs via a passive air sampler (PAS) based on XAD (a styrene–divinylbenzene copolymer) was conducted in 23 different provinces/municipalities/autonomous regions in China, which provides an excellent chance to investigate their occurrences, spatial trends, and potential sources. The total atmospheric concentrations of 13 PFAAs (n=268) were 6.19–292.57 pg m⁻³, with an average value of 39.84±28.08 pg m⁻³, which were higher than other urban levels but lower than point source measurements. Perfluorooctanoic acid (PFOA) was the dominant PFAA (20.6 %), followed by perfluorohexanoic acid (PFHxA), perfluorooctane sulfonate (PFOS), and perfluoroheptanoic acid (PFPeA). An increasing seasonal trend of PFAA concentrations was shown as summer < autumn < spring < winter, which may be initiated by stagnant meteorological conditions. Spatially, the content of PFAAs displayed a declining gradient trend of central China > northern China > eastern China > north-eastern China > south-western China > north-western China > southern China, and Henan contributed the largest proportion of PFAAs. Four sources of PFAAs were identified using a positive matrix factorization (PMF) model, including PFOS-based products (26.1 %), products based on PFOA and perfluorononanoic acid (PFNA; 36.6 %), degradation products of fluorotelomer-based products (15.5 %), and an unknown source (21.8 %).