This protocol describes a step-by-step guide for sampling Volatile Organic Compounds (VOCs) from the headspace/rhizosphere for synthetic blends and biological samples using polydimethylsiloxane (PDMS) silicon tubing, based on methods reported in Thomas et al. (2024) and Vuts et al. (2020). The advantages of using solvent elution when sampling headspace with PDMS tubing are that a liquid sample is generated, which can be used for multiple chemical (e.g. Gas Chromatography/coupled GC-Mass Spectrometry/Nuclear Mass Resonance Spectroscopy), behavioural (e.g. olfactometry) and electrophysiological (e.g. GC-electroantennography) tests, enabling a potential link to be established between VOC content and biological activity.