Korea Ministry of Environment (KMOE) promulgated POPs Control Act in 2008 and have begun to conduct Korea National POPs monitoring program by Korea Environment Corporation (K-eco) as the part of the Korea National Implementation Plan (NIP). The ambient air samples were collected from 38 sites where located over the Korea peninsula, samples were collected every four season. The sampling sites were sorted by four categories; background, rural, urban and industrial along with sampling sites characteristics. PCDD/DFs emission showed sharp decreasing from 880.2 g I-TEQ/S㎥ in 2001 to 24.2 g I-TEQ/S㎥ in 2015, it is only 2.7 % compared with in 2001 emission. This massive decrease of PCDD/DFs emission result of strengthened PCDD/DFs legal emission limit in 2006. Decreasing level of emission mostly affects the decreasing trend of PCDD/DF and dl-PCBs levels in the ambient air. Republic of Korea has environmental ambient air quality standard which is 0.6 pg I-TEQ/S㎥, the annual mean concentration of PCDD/DFs in 2017 is only 2.3 % of Korea environmental ambient air quality, and it is fairly low compared with environmental quality.