Measurement of toxicologically relevant Polychlorinated biphenyl (PCB) congeners such as non-ortho (IUPAC#) 77, 81, 126 and 169 and mono-ortho 105, 114, 118, 123, 156, 157, 189 and di-ortho 170, 180 and Polybrominated diphenyl ethers (PBDEs) such as 47, 66, 85, 99, 100, 138, 153, 154 in environmental samples become almost mandatory in several countries now. However, there is little or no actual data on these compounds in Korean environment and there is no regulatory policy either. Additionally, most of the available methods on these conmpounds involve expensive instrumentations such as HRGC-HRMS or ECNI-LRMS, apart from expensive extraction and clean-up (large volume of solvents) steps. Hence, we developed an electron donor-acceptor high-performance liquid chromatography (HPLC) and high resolution gas chromatography -ECD method as an inexpensive but accurate technique for the determination of these compounds. This add-on step was effectively used with our large environmental sample archive that includes coastal sediments, bivalve mollusks, pine needle and Mongolian Oak leaves from industrial, residential and harbour zones of Korea. Our survey showed the ubiquitous presence of these chemicals in all the matrices analysed. Though the present level of contamination is not alarming, considering the fact that Korea’s economic future is with electronic industries, the likelyhood of emission will increase. Parts-per-trillion level contamination of PBDEs and co-planar congeners is lower than overall PCB contamination. However, the early trend indicates that PBDEs in Korea may emerge as an environmental problem in the near future.