The temporal variations of the 55 Volatile Organic Compounds (VOCs) concentration level and their profiles from 2007 to 2021 in Bulgwang, Seoul and Danggam, Busan in South Korea were assessed along with the emission inventory data to evaluate the effectiveness of the air quality management policies. The concentration of the sum of 55 VOCs at Seoul has decreased 53% from 2007 (32.5 ppb) to 2021 (15.2 ppb) and that of BTEX* (benzene, toluene, and xylenes) has decreased 56% from 2007 (5.2 ppb) to 2019 (2.3 ppb), respectively. The benzene concentration has been lower than 5 μg/m3 since 2007, the national ambient air quality standard value. In the national emission inventory, the VOC emission in Seoul has decreased 32% while that in the Community Emissions Data System (CEDS) has increased 5% during the same period. In Danggam, the 55 VOCs concentration decreased 51% while the emission amount of Busan decreased 6%. It was found that the major emissions sources of VOCs in the national emission inventory was solvent usage while in the receptor modeling results it was mobile sources for the studies in Seoul. These suggest that the VOC emission inventory data need to be improved by using more realistic updated emission factors. Additionally, managing VOCs emission to the Secondary Organic Aerosols (SOA) and ozone formation potential, reducing fugitive emissions of VOCs, and reducing human health effect are also suggested.