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• HS-SPME/GC × GC–ToFMS was used for determination of polar death-related VOCs. • First use of zwitterionic polymeric ionic liquids (PIL) for extraction of polar VOCs. • Coatings' extraction efficiency has the following order: PDMS/DVB < PIL < PA < DVB/CAR/PDMS. • PA and PIL provided a good balance representativeness of headspace composition/extraction efficiency. • The 19 polar VOCs were capture from headspace and determined at ng level. Decomposition of bodies generates several types of polar volatile organic compounds (VOCs), whose types, patterns and ratios change during the various stages of decomposition and, therefore, their determination has huge potential to provide useful information to disclose events related to the time of death, or body surrounding environment. As sample preparation is a mandatory key-point in a method development, this research aims to develop a simple, accurate and rapid approach to study death-related polar VOCs based on headspace solid-phase microextraction (HS-SPME) combined with comprehensive two-dimensional gas chromatography-time of flight mass spectrometry (GC × GC-ToFMS) analysis. The performance of zwitterionic PIL-based fibers (containing a [VIm+C 9 COO− monomer and a [(VIm) 2 C1 2 2+-2Br− crosslinker), tailored for polar compounds, was evaluated for a set of 19 analytes associated with the unique odour created by decomposing bodies, and it was compared to the commercially-available fibers: divinylbenzene/carboxen/poly(dimethylsiloxane) – DVB/CAR/PDMS, poly(dimethylsiloxane)/divinylbenzene – PDMS/DVB and polyacrylate (PA). Fibers with absorptive-type mechanism, such as PA and PIL, showed the best results in the balance of the parameters studied, being able to detect analytes at ng level and providing a profile representative of the headspace composition, thus they may represent a useful tool to respond to current challenges in forensic taphonomy. The reproducibility (with relative standard deviation lower than 18%, depending on the analyte) and relative recoveries (higher than 99.1%) were similar and acceptable for both fibers. The zwitterionic PIL, with ca. 4 times smaller film thickness than PA, still has potential to have the best performance, supported by the efforts to obtain thicker sorbent coatings. [ABSTRACT FROM AUTHOR]