A novel molecularly imprinted polymer (MIP) based on a silica-gel surface for the separation and concentration of polybrominated biphenyls (PBBs) was prepared using 3,3′,5,5′-tetramethylbenzidine (TMB) as a dummy template by a surface molecular imprinting technique in combination with a sol–gel process. The results obtained from a series of adsorption experiments proved that the prepared sorbent had a good adsorption capacity and a fast mass transfer rate to TMB. Meanwhile, a method was developed for the determination of six PBBs using TMB-MIP as a solid-phase extraction (SPE) enrichment sorbent coupled to GC-ECD. Under the optimum experimental conditions, the linear range of the calibration curve was 0.01–5.0 μg L⁻¹ (r² > 0.99), and LODs for each analyte were between 2.0 ng L⁻¹ and 8.0 ng L⁻¹. Relative standard deviations (RSD) for nine replicate detections of 1.0 μg L⁻¹ of each analyte ranged from 4.30% to 7.89%. The proposed method was applied to the determination of six PBBs in spiked water and fish samples with recoveries ranging from 61.48% to 114.06%.