A stir-bar sorptive extraction (SBSE) method followed by automated thermal desorption (ATD) coupled to gas chromatography–mass spectrometry was optimized for determining trace levels of 18 synthetic fragrances (musks). Using the method developed a retention time locked library is created and converted to a screening database. This homebuilt database can be combined with deconvolution software for the identification of musks. A factorial design was provide to evaluate the main parameters and interactions between the factors affecting the process of SBSE. Operating with de MS-detector in the full-scan mode, high sensitivity with detection limits in the low ng L −1 range, and good linearity and repeatability were achieved for all musks. The applicability of the method developed was tested in natural waters (surface and groundwater) and wastewater of a plant treatment (WWPT). The results obtained confirmed the usefulness of the proposed method for the determination and unequivocal identification of musks. This approach enables the developed method to be used for routine screening of environmental samples and posterior rapid quantitation of the positive samples.