Objectives The aim of this study was to identify the health and environmental risk factors of air contaminants that influence environmental and respiratory diseases in Gyeongju, Pohang and Ulsan in South Korea, with a focus on volatile organic compounds (VOCs). Methods Samples were collected by instantaneous negative pressure by opening the injection valve in the canister at a fixed height of 1 to 1.5 m. The sample that was condensed in -150℃ was heated to 180℃ in sample pre-concentration trap using a 6-port switching valve and it was injected to a gas chromatography column. The injection quantity of samples was precisely controlled using an electronic flow controller equipped in the gas chromatography-mass spectrometer. Results The quantity of the VOC emissions in the industrial area was 1.5 to 2 times higher than that in the non-industrial area. With regards to the aromatic hydrocarbons, toluene was detected at the highest level of 22.01 ppb in Ulsan, and chloroform was the halogenated hydrocarbons with the highest level of 10.19 ppb in Pohang. The emission of toluene was shown to be very important, as it accounted for more than 30% of the total aromatic hydrocarbon concentration. Conclusions It was considered that benzene in terms of the cancer-causing grade standard, toluene in terms of the emission quantity, and chloroform and styrene in terms of their grades and emission quantities should be selected for priority measurement substances.