This study was designed to investigate the characteristics of atmospheric concentrations of toxic volatile organic compounds (VOCs) in Korea. Target compounds included 1,3-butadiene, aromatics such as BTEX, and a number of carbonyl compounds. In this paper, as the first part of the study, the performance of sampling and analytical methods was evaluated for the measurement of selected VOCs and carbonyl compounds in the ambient air. VOCs were determined by the adsorbent tube sampling and automatic thermal desorption coupled with GC/MSD analysis, while carbonyls by the DNPH-silica cartridge sampling with HPLC analysis. The methodology was investigated with a wide range of performance criteria such as repeatability, linearity. lower detection limits, collection efficiency, thermal conditioning, breakthrough volume and calibration methods using internal standards. In addition, the sampling and analytical methods established in this study were applied to real field samples duplicately collected in various ambient environments. Precisions for the duplicate samples appeared to be comparable with the performance criteria recommended by USEPA TO-17. The overall precision of the sampling and analytical methods was estimated to be within 20 ∼ 30% for major aromatic VOCs such as BTEX, whereas the precision for major carbonyl compounds such as formaldehyde and acetaldehyde was within 10 ∼ 20% for field samples. 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.