In this paper, dummy molecularly imprinted polymer (DMIP) for tetrabromobisphenol A (TBBPA) was prepared with a sol–gel process on the surface of micro-nano silica particles. Tetrachlorobisphenol A was chosen as the dummy template to avoid TBBPA bleeding. The adsorption characteristics of the DMIP for TBBPA were investigated. The DMIP for TBBPA had a large adsorption capacity (230 μmol g⁻¹), which was about 6 times as much as that of the non-imprinted polymer, fast binging kinetics (20 min) and high selectivity for TBBPA. A method for the determination of trace TBBPA in environmental water samples was established by high performance liquid chromatography coupled with solid phase extraction using the DMIP as sorbent. Under the built method, the linear range of TBBPA standard aqueous solution was 0.2–8.0 ng mL⁻¹ with a correlation coefficient of 0.9947 and the limit of detection was 0.1 ng mL⁻¹. The recoveries at 1.0 ng mL⁻¹ of TBBPA spiked with water samples were in the range of 91–93% and the relative standard deviations were all less than 9.0% (n = 5). The results showed that the properties of the DMIP were superior and could be used to separate and enrich trace TBBPA in environment water samples.