Perfluorinated compounds (PFCs) are of special concern due to their environmental persistence and biotoxicity. In the present study, spatial distribution of PFCs in atmosphere of the Pearl River Delta (PRD) of Southern China was investigated from November 2013 to January 2014. Forty-two air samples were collected using passive air samplers to determine the 13 target analytes, including perfluoroalkyl carboxylic acids (PFCAs, C5-14) and perfluoroalkyl sulfonic acids (PFSAs, C4, C6, and C8). Results showed that the total concentrations of PFCs (ΣPFCs) ranged from 53.7 to 225pgm-3 with an average level of 122 ± 41.5pgm-3, indicating a wide variation on ΣPFCs in atmosphere of the PRD. Perfluorooctane sulfonate (PFOS) was the most abundant PFCs, followed by perfluorooctanoic acid (PFOA), perfluoropentanoic acid (PFPeA), and perfluoroheptanoic acid (PFHpA). PFOS, PFOA, PFPeA, and PFHpA accounted for 26%, 22%, 21%, and 19% of ΣPFCs, respectively. A general decline in ΣPFCs was observed in the atmosphere from south PRD to north PRD. It was likely related to the industrial distribution, population density, and wind direction. In addition, the same order of magnitude of PFOS and lower level of PFOA were observed in this study compared with those in atmosphere sampled in other regions. The lifetime risk indexes on the PFOS and PFOA concentrations were much less than unity, suggesting a lower nononcogenic risk to residents in the PRD.