A highly chlorinated flame retardant, Dechlorane Plus (DP), was measured in five fish species collected in 2008 from 22 river sites across South Korea. The sites consisted of 15 urban-industrial areas, three rural-industrial areas, and four rural rivers. Both syn- and anti-DP isomer were consistently detected in all fish samples regardless of sampling sites and fish species. DP has become a widespread environmental pollutant in South Korea. Concentrations of summation operatorDP isomers ranged from 0.61 to 126ngg(-1) lipid, with a mean concentration of 24.5ngg(-1) lipid. The mean summation operatorDP concentrations in the 15 urban sites (36.1+/-35.3ngg(-1) lipid) were approximately 25 times greater than those measured in the rural sites (1.4+/-1.0ngg(-1) lipid). The summation operatorDP concentrations in this study exceeded those determined in fish from the Great Lakes. DP exposure to fish is related to urbanization activity. Specific urban areas could be significant source areas of DP exposure, even in the absence of a local DP manufacturing facility. Concentrations of syn- and anti-DP isomer ranged from 0.17 to 30ngg(-1) lipid and 0.44 to 97ngg(-1) lipid, respectively. The anti-DP isomer was dominant in all samples. However, the mean f(anti) value for urban-industrial samples (0.67+/-0.060) was significantly lower than that of the technical DP standard (f(anti)=0.75; p=0.032). This observation supports that DP isomers exhibit different bioaccumulation behaviors and that syn-DP isomer more easily accumulates in biota samples than anti-DP isomer does.