Purpose Pyrogenic organic matter (PyOM) in the soil of a maritime pine forest in Central Italy, formed during a fire of high severity, was characterised by Fourier transform infrared (FT-IR) and 13C nuclear magnetic resonance (NMR). Furthermore, soil samples from burnt and unburnt sampling sites and natural charcoal collected from the ground were characterised after progressive heating under air and nitrogen atmosphere. The aim was to better understand the role fire plays on PyOM formation and oxidation. Materials and methods The top 10 cm of mineral soil and the above-lying charcoal particles were collected soon after the fire. Sampling was also performed on an adjacent unburnt portion of the forest. The bulk soil organic matter (SOM), its extractable fraction and charcoal particles were investigated by FT-IR and 13C NMR spectroscopies. They also underwent thermogravimetric analysis under air or N2, stopping the thermal reactions at the end of the first exothermic reaction in the range 350–500 °C. Results and discussion The NMR investigation clearly revealed a significant enrichment in aromatic and alkyl C in the burnt soil compared to the unburnt one. Several clues led to hypothesise that SOM was not exposed to extreme heating during the fire, notwithstanding the high fire severity estimated by a vegetation-based visual scale. In the thermal treatment mimicking fire, charcoal lost much of its mass and carbon content. However, at 500 °C, it still maintained a significant recalcitrant fraction. Nitrogen concentration in the bulk soil increased after heating, particularly under air condition. This phenomenon could be due to the formation of heterocyclic nitrogen compounds in the charred material. Conclusions In the study area, PyOM is rich in aliphatic compounds presumably because of the understory sclerophyllous vegetation typically found in Mediterranean environments. A large fraction of the charcoal released to the soil during the fire is sensitive to oxidation by subsequent fires. On the other hand, charcoal preserves a significant fraction of C, the most recalcitrant one, with expected long residence time in soil. PyOM formed under high oxygen availability is richer in N than that formed in inert atmosphere, which might make PyOM more susceptible to biochemical degradation.