Volatile organic compounds (VOCs) are a complex group of chemicals that pose a direct risk to human health. They also lead to the formation of other air pollution constituents, including fine particulate matter (PM2.5) and ground level ozone (O₃). The ambient air concentrations of 19 VOCs were measured using multi-day 24 h sampling at two urban sites and two rural sites in the area of Khon Kaen, Thailand. Results showed that most VOCs were at concentrations considered acceptable according to the 24 h average standards established by the Thai Pollution Control Department. The VOC acrolein, however, was detected at concentrations (0.69–1.15 μg/m3) in excess of the 24 h average standard (0.55 μg/m3). Two other VOCs, benzene and 1,3-butadiene, were also detected at elevated levels (1.73–2.75 and 0.18–0.40 μg/m3, respectively) that indicated the potential to exceed the 1-year average standard. VOC concentrations were highest in the urban market monitoring site, suggesting that vehicle exhaust and food preparation using cooking oil at high temperatures may have been potential sources of the elevated VOCs.