This study was carried out to evaluate the performance of a sampling and analytical methodology for the measurement of selected volatile organic compounds (VOCs) in the ambient air. VOCs were determined by the adsorbent tube sampling and automatic thermal desorption coupled with GC/FID and GC/MSD analysis. Target analytes were aromatic VOCs, including BTEX, 1,3,5-and 1,2,4,-trimethylbenzenes(TMBs), and naphthalene. The methodology was investigatedwith a wide range of performance criteria such as repeatability, linearity, lower detection limits, collection efficiency, thermal conditioning, breakthrough volume and calibration methods using internal and external standards. standards. Stability of samples collected on adsorbent tubes during storage was also investigated. In addition, the sampling and analytical method developed during this study was applied to real samples duplicately collected in various indoor and outdoor environments. Precisions for the duplicate samples and distributed volume samples appeared to be well comparable with the performance criteria recommended by USEPA TO-17. The audit accuracy was estimated by inter-lab comparison of both duplicate samples and standard materials between the two independent labs. The overall precision and accuracy of the method were estimated to be within 30% for major aromatic VOCs such as BTEX. This study demonstrated that the adsorbent sampling and thermal desorption method can be reliably applied for the measurement of BTEX in ppb levels frequently occurred in common indoor and ambient environments.