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This study was carried out to evaluate the performance of two sampling methods, i.e., adsorbent tubes and canisters, for the measurement of ambient volatile organic compounds (VOCs). A total of 24 target VOCs were selected from a list of 48 priority hazardous air pollutants (HAPs) in Korea. The two sampling methods were investigated with a wide range of performance criteria such as repeatability, linearity, and lower detection limits. In addition, mean relative errors (MRE) and mean duplicate precisions (MDP) were estimated by inter-lab comparison studies for duplicate field samples. Precisions for the two methods appeared to be well comparable with the performance criteria recommended by USEPA TO-15 and TO-17 for canister and adsorbent methods, respectively. Correlations and variations between the VOCs concentrations determined by the two methods were generally good in most cases. However, MREs and MDPs for individual VOCs appeared to be widely ranged, depending on each VOC. This implies that the two methods have its own advantages and disadvantages in determining a variety of VOCs in ambient air, and neither of which has absolute superiority. Finally, 9 of 24 VOCs were found to be difficult to determine by either methods due to their unstability in a canister, and lack of appropriate standard materials. Thus, it is suggested that development of measurement methods for such unstable VOCs is an urgent task from a viewpoint of HAPs management.