The objective of this study was to develop a simple, less time-consuming and accurate sampling technique based on solid-phase sorption with activated carbon as the sorbents. The results from solid-phase sorption techniques were compared to that from a conventional solvent impinger-based technique to confirm the efficacy of the proposed method. The laboratory results indicated that the solid-phase sorption method was suitable for the determination of siloxanes as the measured concentrations were similar to that from a solvent impinge method. The data from solid-phase sorption method showed excellent recovery and reproducibility while the sampling was less labor intensive and less time consuming than the solvent impinge method. Following the laboratory tests, the solid-phase sorption technique was successfully applied to sampling biogas from a field site. This study shows that the activated carbon-based solid-phase sorption can be a reliable and less time-consuming option for the sampling and collection of siloxanes under various different landfill conditions.