Polybrominated diphenyl ethers (PBDEs) are a group of brominated flame retardants, which are manufactured in large quantities and widely used in a variety of consumer goods. Recently they spread ubiquitously as environmental contaminants. In order to investigate the pollution level of PBDEs in different environmental samples, a method has been established by using high resolution gas chromatography coupled with high resolution mass spectrometry (HRGC-HRMS). The method was used to analyze biosamples obtained from the international inter-calibration. The results were satisfactory by analyzing z-score figures. Then, PBDE contents in three samples of sewage sludge were investigated by the method after Soxhlet extraction and multi-layer silica gel chromatographic separation. The number of PBDEs determined was 19. From the results, we can see that the contamination level of PBDEs in the sample from Beijing was higher than those from two other areas. The method was validated and applied for the analysis of environmental samples.