Solid Phase Microextraction (SPME) is a sample preparation and introduction technique in which analytes are extracted into a small volume of extracting phase coated on a fused silica fibre and subsequently desorbed within the analytical instrument. This technique was investigated for the extraction of Volatile Organic Compounds (VOCs) from aqueous matrices and for the determination of phthalate ester leaching from plastic items. Using a 100|am PDMS fibre and GC-MS analysis, VOCs could be determined in water samples at the low parts per billion level. This was found to match Purge and Trap-GC-MS detection limits for most VOCs but with the additional advantage of easier operation, shorter analysis times and potential on-site sampling. PVC toys and childcare articles were screened for leaching of the phthalate ester Diisononyl phthalate (DINP) by shaking a sample disc in a saliva simulant followed by extraction of the leached phthalates. An 85|xm polyacrylate fibre was used to extract the leached phthalates and analysis was carried out using GC-MS. Solvent extraction was carried out for comparative purposes. Articles leaching phthalates above xfig / 1 0cm2 / min could be identified.