Despite concerns to their increasing contribution to ecological and human exposure, the atmospheric levels of poly- and perfluoroalkyl substances (PFASs) have been determined mainly in Europe and North America. This study presents the indoor and outdoor air concentrations of volatile PFASs [fluorotelomer alcohols (FTOHs), and perfluoroalkyl sulfonamides/sulfonamidoethanols/sulfonamide ethyl acetate (FOSAs/FOSEs/FOSEA)] for the first time in Korean cities. In contrast to the good agreement observed for indoor FTOHs levels in Korea and Europea/North America, FOSAs/FOSEs levels were 10–100-fold lower in Korean indoor air, representing a cultural difference of indoor source. Korean outdoor air contained higher PFAS levels than indoor air, and additionally showed different PFAS composition profile from indoor air. Thus, indoor air would not likely be a main contributor to atmospheric PFAS contamination in Korea, in contrast to western countries. Inhalation exposure of volatile PFASs was estimated to be a minor contributor to PFOA and PFOS exposure in Korea.