In this work, we developed a novel graphene-assisted matrix solid-phase dispersion (GA-MSPD) method for extraction of polybrominated diphenyl ethers (PBDEs) and their methoxylated (MeO-) and hydroxylated (OH-) analogs from environmental samples. We found that grinding the solid sample with chemically converted graphene (CCG) powder yielded a tight contact and sufficient dispersion of the sample matrix due to the large surface area and flexible nanosheet morphology of CCG. The resultant blend was eluted using a two-step elution strategy: PBDEs and MeO-PBDEs were eluted firstly by hexane/dichloromethane and analyzed by GC-ECD, and then OH-PBDEs were eluted by acetone and determined by LC-ESI-MS/MS. The GA-MSPD conditions were optimized in detail. Better recoveries were obtained with GA-MSPD than with other sorbents (C18 silica, Florisil and carbon nanotubes) and other extraction techniques (Soxhlet and accelerated solvent extraction). Other advantages of GA-MSPD, including reduced consumption of sorbent and solvent, good selectivity and short extraction time, were also demonstrated. In analysis of soil samples, the method detection limits of five PBDEs, ten MeO-PBDEs and ten OH-PBDEs were in the range of 5.9-28.7, 14.3-46.6, and 5.3-212.6 pg g(-1) dry weight, respectively. The proposed method was successfully applied to the extraction of PBDEs, MeO-PBDEs and OH-PBDEs from different kinds of spiked environmental samples, including soil, tree bark and fish.