Since being recognised as a potential emissive source, plastics in heritage collections are being investigated to understand the chemical compounds they release and how they might affect the stability of other heritage objects. There is a requirement for non-invasive methods of analyses to identify unknown plastics and the emitted volatiles they generate. Therefore, Tenax-TA sampling tubes were used to collect the emitted volatiles from 41 samples of 9 polymer types of varying formulation, provenance and age. Thermal desorption-gas chromatography coupled with mass spectrometry (TD-GC/MS) has been successfully used to separate and identify the emissions of the 41 samples at 23 °C, after heating to 70 °C and after accelerated degradation.