Tetrabromobisphenol A (TBBPA) in water from Xiongan New Area was determined by gas chromatography-mass spectrometry (GC-MS), simultaneous with its risk assessment. The optimal extraction conditions, derivatization factors (such as derivation reagent amount, derivatization time and temperature), and dissolution solvent were determined by orthogonal experiment. These results indicated the optimum derivatization time and temperature were 70 °C and 30 min, respectively, whilst the amount of derivatization reagent (N,O-bis (trimethylsilyl) trifluoroacetamide) was 40 μL. The optimum extraction efficiency was obtained when using the mixture of hexane-dichloromethane (1:1, v:v) with salt concentration of 6 g/L. Using the sample of S9 as control, the recovery experiments were performed with three different spiked levels. The water samples of Baiyang Lake and Fuhe river were analyzed using the optimized conditions. Those results showed that the concentrations of TBBPA in samples ranged from 18.5 ng/L to 82.6 ng/L, which lies in the middle level of data previously published from other areas in China. The risk quotient (RQ) model was used to evaluate the above data. The results of exposure and risk assessment showed that the margin of exposure (MOE) was 1.28 × 10⁷-2.5 × 10⁷ and the RQ_max was 0.0266. The European Food Safety Authority (EFSA) standard and categories of RQ indicates that the estimated dietary exposure to TBBPA is unlikely to raise significant health concerns. This is the first report on the occurrence and risk assessment of TBBPA in waters from Xiongan New Area, which will be helpful for further risk assessment of other persistent organic pollutants. At present, the toxicological data of TBBPA in the biological body of Baiyang Lake is limited. In addition, more accurate and convenient approaches for the risk assessment of TBBPA should be explored.