Stir bar sorptive extraction and liquid desorption (LD) followed by large volume injection and capillary gas chromatography coupled to mass spectrometry (SBSE-LD-LVI-GC-MS), had been applied for the determination of ultra-traces of eleven polybrominated diphenylethers (PBDEs), from tetra to nona congeners (BDE-47, BDE-100, BDE-99, BDE-85, BDE-154, BDE-153, BDE-183, BDE-197, BDE-196, BDE-207 and BDE-206), in environmental matrices. Instrumental calibration under the selected-ion monitoring (SIM) mode acquisition and parameters that could affect the SBSE-LD efficiency are fully discussed. A complete randomized factorial design was established for the first time to optimize the main experimental parameters that affecting the SBSE-LD efficiency, including decisive interactions, which provides a more realistic picture of the sampling process. The analysis of variance (ANOVA) was the statistical method used to analyze data. From the data obtained, it can be emphasized that experimental parameters such as extraction time (240 min), agitation speed (1250 rpm), methanol content (40%) and desorption conditions (acetonitrile, 15 min), were the best analytical compromise for the simultaneous determination between tetra and nona congeners in aqueous media. A remarkable recovery (65.6-116.9%) and repeatability (<12.1%) were attained, whilst the experimental data allowed very good agreement with predict theoretical equilibrium described by the octanol-water partition coefficients (K(PDMS/W) approximately = K(O/W)), with the exception of nona congeners since slightly lower yields were measured. Furthermore, excellent linear dynamic ranges from 0.01 to 14.0 microg/L (r2>0.9917) and low detection limits (0.3-203.4 ng/L) were also achieved for the eleven congeners studied. The proposed methodology was applied for the determination of ultra-trace levels of PBDEs in waste water, sediments and printed board circuit matrices by the standard addition approach, showing to be reliable, sensitive and having a low sample amount requirement in compliance with the international regulatory bodies.