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Stir bar sorptive extraction (SBSE) is a sample preparation technique that involves the extraction and enrichment of organic compounds from a liquid sample. The present study focused on the determination and assessment of phenolic xenoestrogens exposure. Firstly, the determination of octylphenol (OP), nonylphenol (NP) and bisphenol A (BPA) in river water samples by SBSE and thermal desorption (TD)/gas chromatography mass spectrometry (GC/MS) was developed. The limits of detection (LODs) of OP and NP were 2 and 20ng L^<-1>, respectively. On the other hand, the LOD of BPA was 0.5μg L^<-1>. Secondly, a simultaneous analysis of phenolic xenoestrogens, such as OP, NP, BPA, dichlorophenol (DCP), butylphenol (BP) and pentachlorophenol (PCP) in river water samples by SBSE with in situ derivatization and thermal desorption (TD)/gas chromatography mass spectrometry (GC/MS) was developed. The LODs of phenolic xenoestrogens in water samples were 0.5〜5ng L^<-1>. A highly sensitive analysis was achieved by using SBSE with in situ derivatization method. Thirdly, the SBSE with in situ derivatization method was applied to measure phenolic xenoestrogens in human urine sample. The LODs of phenolic xenoestrogens in human urine samples were 0.01〜0.05ng mL^<-1>. In addition, the quantity of phenolic xenoestrogens in human urine samples was obtained. Exposure assessments of phenolic xenoestrogens could be performed.