AbstractGas chromatography coupled to quadrupole ion storage mass spectrometry (QISTMS) operating in the non‐resonant mode is presented as an innovative approach for the analysis of selected polybrominated diphenyl ethers (PBDEs). Although reductions in complexity and time needed for optimization are achieved in comparison with the resonant option, precise adjustment of the mass spectrometric conditions is required. Differences in isolation and fragmentation patterns of target species with degree of bromination were observed. The reliability of the method was confirmed by using standard solutions through the evaluation of certain quality parameters such as accuracy (92–108%), injection repeatability and reproducibility (coefficient of variation below 10% and 15%, respectively). Detection limits ranged from 62 to 621 fg, providing sensitivity similar to that of negative chemical ionisation (NCIMS) and greater than that of electron ionization mass spectrometry. The applicability of QISTMS method to real samples and matrix effects were evaluated through the analysis of some PBDE congeners in a sewage sludge sample from a Spanish waste‐water treatment plant. Comparable results were obtained using QISTMS and NCIMS. According to these observations, QISTMS performed in the non‐resonant mode may constitute a low‐cost, rapid and reliable alternative to high‐resolution devices for the analysis of selected PBDEs in environmental samples. Copyright © 2004 John Wiley & Sons, Ltd.