The extraction efficiency of pressurised liquid extraction (PLE), microwave-assisted extraction (MAE), and ultrasonic-assisted extraction (UAE) under different conditions has been compared for the recovery of the most commonly employed brominated flame retardants (BFRs) from styrenic polymeric matrixes. A HPLC-MS/MS method has been proposed for the simultaneous separation and quantification of tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD) diastereomers, and decabromodiphenyl ether (deca-BDE) in the polymeric extracts. PLE results in complete extraction of TBBPA and HBCD (95-100% recovery), and intermediate recovery rates for deca-BDE (50%). MAE, on the other hand, gives comparable performance to PLE for HBCD, but lower extraction yields for TBBPA and mainly deca-BDE. Ultrasonication, finally, offers relatively low extraction recoveries (10-50%). The proposed analytical procedures could be used for the effective identification and quantification of BFRs in styrenic plastics and for quality purposes in recycling facilities that deal with styrenic fractions from waste electrical and electronic equipment (WEEE).