In this study, we attempt to analyze for 4 compounds (MEK, MIBK, n-Butyl acetate, i-Butyl alcohol) in ambient air using on-line thermal desorber (on-line TD) with gas chromatograph/flame ionization detector (GC/FID). These compounds will be regulated by KMOE (Korean ministry of environment) within 2010. We tested two different experimentation. First, we try to find the influence of Nafion dryer for the 4 compounds. Second, we want to know basic analytical characteristic of target compounds through the linearity, reproducibility, and minimum detection limit. According to this study, target compounds are removed in Nafion dryer more than 80 percent, respectively. So, we progressed next experimentation progressed without Nafion dryer using hydrophobic cold trap. Results for each compounds showed good linearity (r²＝0.99 upper) and good precision (RSD＝1 % below). In additional, we analyzed the ozone precusors standard gas (56 compounds) using the same method to see if there are any peaks to be overlapped in ambient air. These results showed that there is no peak overlapped. This means that analytical system of this study could be used on-line analytical system. Minimum detection limit (MDL) value for this system are less than minimum malodor threshold concentration.