Abstract: Per- and polyfluoroalkyl substances (PFASs), a class of man-made organic chemicals containing at least one C-F bond, have been produced and widely used for more than 70 years due to their unique physicochemical properties. Their environmental pollution problems are of great concern in consideration of their bioaccumulation, toxicity, and long-distance transport potential. Numerous studies have shown that PFASs are ubiquitous in different environmental matrices around the world. The environmental behavior of PFASs in aquatic systems has been extensively studied. Limited studies of PFASs in the atmosphere showed that atmospheric environment, as an important medium for the transport and transformation of PFASs, has an important impact on the long-distance transport and environmental risks of PFASs. This paper summarized the literature on the existence, sources, and distribution of PFASs in the atmospheric environment and human exposure to PFASs through indoor and outdoor air and dust in order to provide a reference for the environmental behavior and risk assessment of PFASs in the atmosphere. Additionally, the future perspective of related research was also discussed. It was found that the relevant studies have mostly focused on emission characteristics of PFASs from the point sources associated with their production, use and disposal, and the impact on the surrounding environment. Ionic PFASs (i-PFASs) were usually the main compounds in the atmospheric particulate phase, while neutral PFASs (n-PFASs) were predominant in the gas phase. N-PFASs were generally dominated by fluorotelomer alcohols (FTOHs). The contamination of i-PFASs varied by different sites and regions. In recent years, the contribution of short-chain PFASs to the total concentrations of PFASs in the atmosphere was gradually increased. PFASs in the atmosphere could be removed via wet and dry deposition, with wet deposition accounting for a larger proportion. Compared with dietary intake, the intake via dust ingestion and inhalation contributed less for non-occupational population exposure to PFASs. Nevertheless, the higher risks of PFAS exposure via dust ingestion for children and via inhalation for some occupational populations deserve further attention.