Having been largely used in industrial and household products, perfluoroalkyl acids (PFAAs) appear in environmental and biological systems with prevalence and persistence and have raised great concern in recent years. The present study is aimed at studying concentrations and composition profiles of 16 PFAAs in surface sediments collected from 51 sampling locations in 4 main rivers of the Pearl River Delta, one of the economy-developed areas in China. The total PFAA concentrations (∑ PFAAs) were determined in a wide range of 1.89-15.1 ng g(-1) dw (dry weight) with an average concentration to be 3.54 ng g(-1) dw. Higher ∑ PFAAs were observed in the downstream of Dongjiang River and the Pearl River, possibly due to the discharge of industrial wastewater. Perfluoropentanoic acid (PFPeA) and perfluorooctane sulfonate (PFOS) were the dominant PFAAs, accounting for 51 to 85% of ∑ PFAAs in 27% of the samples. High PFPeA concentrations in sediments of urban river were scarcely observed in previous studies worldwide. The sources of short-chain perfluoroalkyl carboxylic acids (PFCAs) were significantly different from those of other PFAAs. Preliminary hazard assessment proved negligible for PFOS, perfluorooctanoic acid (PFOA), PFPeA, and perfluorohexanoic acid (PFHxA) concentrations in sediments from rivers of the Pearl River Delta.