Air pollution from the Daegu industrial complex (Die) in Korea has been a common nuisance and cause of complaints for nearby residents. The current study measured the indoor and outdoor levels of six VOC (benzene, toluene, ethylbenzene, and three isomeric xylenes) at two residential areas with a different proximity to the ODIC, plus the ambient levels at two industrial areas within the boundary of the DDIC. The QA/QC program included the range of correlation coefficient (0.94-0.99) for calibration curves, within the permissible range. Toluene was the most abundant VOC in the ambient air both in residential and industrial areas. Both indoor and outdoor air concentrations of all target VOC except benzene were higher in residential area near the DIC compared to that further away from the DIC. Moreover, the ambient air concentrations of all target VOC except benzene for two industrial sites (A and B) were significantly higher than the outdoor or indoor air concentrations in the two residential areas. The findings further suggested that VOC ambient levels measured in a residential area near the DIC be used as a potential indicator of odor-causing unidentified air pollutants transported from the DIC. Moreover, it was found that the elevated ambient toluene levels outweighed the indoor sources with respect to the environmental exposure of residents nearby the DIC. However, in the residential area further away from the DIC, the toluene indoor sources outweighed the outdoor sources.