An analytical methodology based on thermal desorption and comprehensive two-dimensional gas chromatography with dual time-of-flight mass spectrometry and flame ionization detection (TD-GC × GC-TOFMS/FID) has been developed for non-target analysis of volatile organic compounds (VOCs). The technique was optimised for the measurement of the VOC content of the particulate phase (PP) fraction of aerosols produced by a tobacco heating product (THP1.0) and 3R4F mainstream tobacco smoke (MTS). The method involves sampling the PP fraction on quartz wool packed in a sorbent tube directly connected to machine-puffing, followed by a dilution through a TD recollection procedure over Tenax/Sulficarb sorbent before TD-GC × GC-TOFMS/FID analysis. The comparison of the VOC content of the PP fraction of aerosols produced by THP1.0 and MTS highlighted the compositional difference between tobacco combustion (592 peaks) and tobacco heating process (160 peaks). Mass spectrometric signals were used for qualitative analyses based on linear retention indices, mass spectral matches, and GC × GC structured chromatograms, which collectively identified up to 90% of analytes detected in PP samples. FID signals were used for semi-quantitative analyses based on a chemical class external calibration method. The global chemical composition of PP samples showed that hydrocarbons, oxygenated, and nitrogen-containing compounds were fewer in number and much less abundant in THP1.0 PP. Overall, 93 compounds were common to the two sample types. Excepted for a few highly volatile compounds (mainly furan family) as well as glycerine and its acetate, analyte concentrations were higher in MTS PP. Copyright © 2019 Elsevier B.V. All rights reserved.