This study investigated the particle size distribution and atmospheric transport potential of perfluoroalkyl carboxylic acids (PFCAs) and certain perfluoroalkyl ether carboxylic acids (PFECAs) emitted from a mega fluoropolymer industrial park (FIP) in China. Ambient aerosols sampled in a residential area near the FIP were separated by a cascade impactor into five size fractions (<0.15 to 12.15 μm). Homologues of PFCAs (C5-C11) and five PFECAs were frequently detected in the samples (detection frequencies 40-100%), albeit not in all size fractions. Perfluorooctanoic acid (PFOA) exhibited the highest concentrations (6.5 to 2900 pg m-3). A noticeable mass mode in the >1 μm size range was observed for PFCAs and PFECAs in the samples that were directly influenced by wind from the direction of the FIP. Based on the PFOA concentrations in the aerosol samples, the emission rate of PFOA to air from the FIP was estimated to be 0.4-1.3 t year-1. Modeling results demonstrated that around 67% of the PFOA air emission was transported in the atmosphere above 1500 m in a 7 day continuous emission scenario, implying that the PFOA on <12.15 μm particles undergoes long-range atmospheric transport after being emitted from the FIP.