Passive samplers have been widely used for volatile organic compounds determination. Following the green chemistry tendency of the direct determination of adsorbed compounds in membrane-based devices through using head space direct chromatography analysis, this work has evaluated the use of Amberlite XAD-2, XAD-4, and XAD-16 adsorbents as a filling material for passive samplers. Direct analysis of the membranes by HS-GC-MS involves a solvent-free method avoiding any sample treatment. For exposed membranes, recoveries ranged from 10% to 203%, depending on the compound and adsorbent used. The limit of the detection values ranged from 1 to 140 ng per sampler. Acceptable precision and sensitivity levels were obtained for the XAD resins assayed.