The main objectives of this study were to identify from literature review the potential sources and to provide a preliminary national emission inventory for the unintentionally produced polychlorinated biphenyls (PCBs) (i.e., by - product PCBs). In Korea, fuel combustion, waste combustion, thermal industrial processes, and transportation were identified as potential sources of by -product PCB s. According to the availability of the emission factors and/or activity data, emission inventory could be assessed only for fuel combustion, waste combustion, steel industry, non-ferrous industry, and non-metallurgical industry. The total national emission of by-product PCBs was estimated to be 1087kg for the year 2000. The preliminary estimation further indicated that the steel manufacturing was the single dominant emission category, contributing 93％ to the total emission. Of the steel manufacturing processes, the contribution of the electric arc furnace was about 80％ of the total emission. Due to high uncertainty associated with both the emission factors and activity statistics, the emission estimates in this study are likely to contain significant errors. However, the results of the present work could serve the first step toward future efforts to establish national source and emission inventories of by-product PCBs.