In recent years, plastics are designated as a source of indoor pollution and particular attention has thus been devoted to the identification of emitting low molecular weight compounds. Headspace-solid phase microextraction-gas chromatography coupled with mass spectrometry (HS-SPME-GC/MS) has been already successfully applied for screening emissions from synthetic materials. This analytical tool being also non-invasive, it has been already successfully applied in the field of cultural heritage science for the identification of volatile organic compounds (VOCs) emitted from various museum objects made of natural materials. In this research, we aimed at assessing the use of HS-SPME-GC/MS as an in situ non-invasive analytical tool for a better knowledge of the volatile organic compounds emitted by plastics in collections. The possibility of characterizing plastics based on their emission signatures was also evaluated. Twelve new standard plastic samples, belonging to seven main polymer families widely present in museum collections as well as three naturally aged museum objects, were investigated. In this paper, we provide a survey of the VOCs emitted, and the use of HS-SPME-GC/MS for identifying volatile marker compounds, degradation products, additives, and monomer residues of the plastic synthesis is evaluated. More than 200 different VOCs were identified from the new standard samples. Two categories of VOCs were distinguished: “non-specific” and “specific” ones. We showed that based on the “specific” VOCs, it was possible to identify the nature of the polymeric matrix itself or at least to unambiguously distinguish a plastic by family. Emissions from the museum objects were then characterised, and main volatile degradation compounds considered as degradation markers of the natural deterioration of polymeric matrices, were identified. This identification procedure could be further exploited for the characterization of VOCs emitted by objects made of multiple synthetic polymers. Complementary to other techniques, this analytical tool is an interesting way to assess the risk for the objects stored in the vicinity of emitting plastics.