In this research, field samplers are developed using polydimethylsiloxane (PDMS) thin-film as the extraction phase. This technique is based on a similar theory, the solid-phase microextraction (SPME) technique. More specifically, the development of the field sampler involves cutting a section of PDMS thin-film into a specific size and shape, and mounting it onto a stainless steel wire (the handle). The thin-film is then placed into a protective copper cage prior to deployment to prevent biofouling. Kinetic calibration or equilibrium calibration with the standards in the extraction phase is used to introduce an isotopically labeled internal standard for on-site calibration. The initial loading of the standard onto the thin-film and the amount of standard remaining on the thin-film are determined using gas chromatography-mass spectrometry and subsequently used to estimate the concentration of the target analytes. In addition, the field samplers are deployed in the field at two locations (the Meuse River in Eijsden, The Netherlands from April to May, 2005 and Hamilton Harbour located at the western tip of Lake Ontario, ON, Canada from September to December, 2006). Polycyclic aromatic hydrocarbons are identified, and concentrations of fluoranthene and pyrene are estimated in the low ng/L range. The results from both sampling sites are within the expected ranges for environmental samples. This polymeric extraction phase has a high surface-to-volume ratio compared with SPME, which results in higher sensitivity and mass uptake, leading to the detection of lower levels of analytes that many other techniques are unable to achieve.