Airborne particulate matter (APM) has an important role in inhalation exposure, especially in China. The environmental occurrence of conventional and unknown per- and polyfluoroalkyl substances (PFASs) in APM remains unclear. Therefore, in this study, a two-stage experiment was designed to identify potential PFASs and to investigate their distribution in APM. Indoor and outdoor APM samples were collected from five selected cities in China. Through PFAS homologue analysis and suspect screening, 50 peaks were identified with different confidence levels (levels 1-3). Among the identified PFASs, 34 emerging PFASs including p-perfluorous nonenoxybenzenesulfonate, 6:2 polyfluoroalkyl phosphate diester, n:2 fluorotelomer sulfonates, n:2 fluorinated telomer acids, n:2 chlorinated polyfluoroalkyl ether sulfonic acids, 1:n polyfluoroalkyl ether carboxylic acids (1:n PFECAs), perfluoroalkyl dioic acids (PFdiOAs), hydro-substituted perfluoroalkyl dioic acids (H-PFdiOAs), and unsaturated perfluorinated alcohols (UPFAs) were identified in APM. In particular, 1:n PFECAs, PFdiOAs, H-PFdiOAs, and UPFAs were first detected in APM. Although human exposure to perfluorooctanoic acid via inhaled APM was noted to not be a risk (hazard quotient <0.1) in this study, the expansion of the PFASs screened in APM implies that human exposure to PFASs might be much more serious and should be considered in future risk assessments in China.