Postpyrogenic soil dynamics is an informative tool for studying soil elementary processes in extreme temperature conditions and for predicting short time environmental changes in conditions of catastrophic landscape changes. Soil organic matter (SOM) system evolution is the most rapid process of postpyrogenic soil development. In this relation, the focus on humus structure is important for understanding these important dynamics. Soil restoration after spontaneous forest fires near Togljatty City (Samara Region, Russia) was abandoned in 2010 and further monitoring over the next ten years was organised to evaluate the speed of humus accumulation dynamics. The aim of this study was to apply the 13C-NMR (nuclear magnetic resonance) spectroscopy to analyse the effect of forest fires on SOM degradation in Scotch pine forests on Psamment Entisols of the fragmented steppe in the Samara Region. Three key soil plots were studied for estimating SOM quality changes under the forest fire effect: surface forest fire, crown forest fire and control, i.e. 18 soil samples of top soil horizons were analysed in three replicates. The data obtained indicate that the humus molecular composition was substantially affected by the wildfires. Investigation of the humic acids’ (HAs) molecular structure by 13C-NMR showed a relative increase in aromatic compounds and decrease in aliphatic ones. The aromaticity degree of HA molecules increases in 5.7 and 3.8 times in cases of surface and crown forest fires, correspondingly. In general, crown and surface fires plots are not very different in terms of 13C-NMR spectra of HAs (p = 0.34); however, HAs of control plot have essential differences from pyrogenic ones (p < 0.05). 13C NMR spectra have shown a change in the proportion of oxygen-containing functional groups as well. One of the most important effects observed in wildfire-affected SOM is that the proportion of lignin-like structures increases as a concomitant effect of depletion of C,H-alkyl groups, especially in the case of crown fires.