A methodology for identifying volatile organic compounds (VOC) and determining air quality of indoor air has been developed. The air samples are collected using pump samplers by the inhabitants when they perceive odorous and/or discomfort episodes. Glass multi-sorbent tubes are connected to the pump samplers for the retention of VOC. The analysis is performed by automatic thermal desorption (ATD) coupled with gas chromatography-mass spectrometry (GC/MS). This methodology can be applied in cases of sick building syndrome (SBS) evaluation, in which building occupants experience a series of varied symptoms that appear to be linked to time spent in the building. Chemical pollutants concentrations (e.g., VOC) have been described to contribute to SBS. To exemplify the methodology, a qualitative determination and an evaluation of VOC present were performed in a dwelling where the occupants experienced the SBS symptoms. Higher total VOC (TVOC) value was detected in episodes in indoor air (1.33 ( 1.53 mg/m3) compared to outdoor air (0.71 ( 0.46 mg/m3). The concentrations of individual VOCs, such as ethanol, acetone, isopropanol, 1-butanol, acetic acid, acetonitrile and 1-metoxy-2-propanol, were also higher than the expected for a standard dwelling. The extal source of VOC was found to be a not declared activity of storage and manipulation of solvents located at the bottom of a contiguous building.