The purpose of this study is to evaluate a method for the measurement of N,N-Dimethylformamide (DMF) and to apply the method to the ambient air samples. For the determination of DMF together with other general VOCs (e.g., benzene, toluene, and xylenes), adsorption sampling and thermal desorption with GC/MS was used in this study. The sampling and analytical approaches tested in this study showed a good repeatability and linearity with lower detection limits of less than 0.35 ppb. Field measurements were carried out at three industrial sites (Daegu-Seongseo, Siwha and Banwall industrial complexes) and one residential site in Daegu city during a period from October 2006 to November 2008. DMF was detected in 71.8% of the total samples from the Seongseo industrial complex, well known for textile industry. In contrast, DMF was detected in only 20.4% and 12.9% of all the samples from the other two sites in Banwall and Siwha industrial complexes, respectively. This implies that sources of DMF should be strongly associated with textile industry. The mean concentration of DMF also appeared to be the highest in Seongseo site (5.95 ppb), followed by a residential site in Daegu (3.28 ppb), Banwall (0.88 ppb) and Siwha (0.55 ppb). In this study, we demonstrated the environmental significance of DMF in urban ambient air. To our knowledge, the DMF measurement introduced in this paper is the first case of an official report in Korea.