This study provided baseline data of PFAA pollution in rivers of the PRD, sourthern China. PFBS, PFOA and PFOS were the predominant PFAAs detected in this BIO 1211 study. Higher levels of ∑ PFAAs were found in the water samples collected Jiangmen section of Xijiang River, Dongguan section of Dongjiang River and the Pearl River flowing the cities, suggesting the existences of potential sources in this area. PCA model concluded that short-chain PFAAs (C ≤ 7) and long-chain PFAAs (C ≥ 8) had different sources in the surface water. Among the different PFAA homologues, the average log Koc values generally increased with increasing perfluoroalkyl chain length. The log Kd values for PFAAs with the same carbon chain length on sediment were lower than that on SPM. However, particle/water and sediment/water interactions are very complex and largely controlled by the organic carbon. Overall, these data could help improve understanding the fate of PFAAs and are essential for modeling behaviors of transportation and transformation for PFAAs in water environment.