Fire represents a major threat to Mediterranean terrestrial ecosystems because of the high temperatures reached during summer. While massive loads of organic, inorganic compounds and particulate matter are known to be emitted into the atmosphere from forest wildfires, less is known about the emission from vegetation surrounding fires where air temperatures higher than 100 °C can be reached. Little information exists on the emission from dead vegetation accumulated as litter over forest soils, from which fires often starts. In this study, the response of litter to heatwaves generated by nearby fires was investigated under controlled conditions. Litter samples collected in a Mediterranean maquis and a Holm oak stand during summer were placed in an enclosure flushed with a continuous flow of air, the temperature of the enclosure was progressively risen to 125 °C, until some smog developed but no flaming occurred. The gas from the enclosure was analysed for the content of CO2, H2O, and volatile organic compounds (VOC) to assess the dependence of emission from the air temperature. VOC emission was continuously determined by Proton-Transfer-Reaction mass spectrometry with time of flight (PTR-TOF-MS). Data obtained were complemented with those obtained by collecting VOC on traps that were later analysed by Gas chromatography–mass spectrometry (GC-MS). Results provided useful information to understand the emission mechanism of VOC and other gases from dead vegetation present in the litter of two Mediterranean ecosystems, both dominated by evergreen vegetation species. The study demonstrated that low molecular weight VOC and aromatic hydrocarbons (arenes) produced mostly by thermal oxidation of the wood biopolymers are emitted in addition to isoprenoids typically associated to storage organs and photosynthetic pathway. Moreover, our results support parameterization of litter VOC emission processes in air quality models.