The occurrence, species- and habitat-dependent distribution of brominated flame retardants (BFRs) and PBDE metabolites comprising 27 polybrominated diphenyl ethers (PBDEs), 3 hexabromocyclododecanes (HBCDs), tetrabromobisphenol A (TBBPA), 17 methoxylated (MeO-) BDEs, and 8 hydroxylated (OH-) BDEs were determined in marine environments (sediment and seawater) and 20 biota species in food web in the southern part of Korea. The concentration of HBCDs was statistically higher in both pelagic (5.73-60.1 ng/g lipid weight [lw]) and demersal fish (2.45-31.3 ng/g lw), whereas a higher level of OH-BDEs was observed in benthic invertebrates (2.48-40.7 ng/g lw), suggesting different composition of BFRs and PBDE metabolites between species. The concentrations of TBBPA and MeO-BDEs were significantly higher in pelagic fish (1.31-11.3, 6.15-61.5 ng/g lw) than in demersal fish (not detected [N.D.]-4.45, 0.956-8.52 ng/g lw) and benthic invertebrates (N.D.-8.11, 0.182-4.65 ng/g lw), reflecting a dependence on habitat. Additionally, analogue distribution of PBDEs in pelagic fish was similar to that in seawater, whereas the distribution in demersal fish and benthic invertebrates was similar to the distribution in sediment. The bioconcentration factor (BCF) and trophic magnification factor (TMF) of α-HBCD, some of PBDEs, and 6-MeO-BDE47 were up to 5000 and 1, respectively, suggesting strong bioaccumulation and biomagnification.