A rapid, simple, and sensitive method has been developed for the analysis of bromophenols in tap water and Trachypenaeus curvirostris by using headspace in-tube microextraction (HS-ITME) coupled with capillary electrophoresis (CE). In the newly developed method, simply by placing a capillary filled with a basic run buffer in the HS above an acidic donor solution, volatile acidic analytes were extracted into the acceptor phase in the capillary. After extraction, electrophoresis of the extracts in the capillary was carried out. Extraction parameters such as the extraction temperature, extraction time, pH of the sample solution, ionic strength, and volume of the sample solution were systematically investigated. Under the optimized conditions, enrichment factors for three bromophenols were 812, 685, and 568, respectively. The proposed method provided a good linearity, low limits of detection (below 5.25 ng/mL), and good repeatability of the extractions (RSDs below 7.8 %, n = 6). The tap water and T. curvirostris samples were analyzed by the proposed method, and the obtained results indicated that the proposed method provides acceptable recoveries and precisions.