Polybrominated diphenyl ethers (PBDEs) are widely used as flame retardants. The aim of the present study was to evaluate the PBDE serum levels in residents from an electronic waste dismantling region, residents living within 50 km of the dismantling region, and a referent group with no occupational PBDE exposure. Fourteen PBDE congeners including BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, BDE-183, BDE-196, BDE-197, BDE-203, BDE-206, BDE-207, BDE-208 and BDE-209 were quantified in these three groups by gas chromatography-negative chemical ionization (NCI) mass spectrometry in selected ion monitoring (SIM) mode. We found that the levels of all PBDE congeners in serum of residents from electronic waste dismantling region were significantly higher than those in the two other groups. The referents showed the lowest PBDE levels. Concentrations of congeners with a high number of bromine substituents, i.e., hepta- to decaBDEs in occupational exposure workers were 11-20 times higher than those in the referent group. BDE-209 was the dominant congener. The highest concentration of BDE-209 was observed among the electronic waste dismantling workers, and it was 3436 ng g(-1) lipid weight (ng g(-1) l.w.), which is the highest concentration of BDE-209 in humans worldwide. Some higher brominated PBDE congeners such as BDE-197, BDE-207 and BDE-208 also showed elevated concentrations in dismantling workers. This study confirms that BDE-209 is released to the environment and can bioaccumulate in the blood of electronic waste dismantling workers, and extensive occupational exposure to PBDEs leads to elevated concentrations of all PBDE congeners in serum.