• The structure, proportion and mode of assembly of lignin, celluloses and hemicelluloses have marked effects on the reaction mechanisms during thermal treatment and therefore have a strong influence on the quality of the final product. The effect of treatment conditions, including severe conditions (up to 553 K) and treatment duration (up to 8 h) on the structure of native spruce and beech lignins was studied. • Lignin content was determined by the Klason method and lignin structure was evaluated by thioacidolysis. • The results highlighted the strong reactivity of the native spruce and beech lignins towards severe heat treatments. The distinct susceptibility of syringyl (S) and guaiacyl (G) units towards thermal treatment is confirmed by comparing the data for beech and spruce samples. The most severe treatment of spruce wood (280 ◦ C) induced a dramatic enrichment in lignin content together with the almost complete disappearance of G lignin units, whereas a more moderate treatment substantially changed lignin structure by degradation reactions that affect the p-hydroxyphenyl (H) and G lignin units similarly. • Thioacidolysis revealed that the thermal treatment induces the appearance of vinyl ether structures in spruce lignins. The decreased yield of the G and S thioacidolysis monomers reflects the progressive disappearance of G and S lignin units only involved in β-O-4 bonds and the formation of condensed linkages in proportions related to treatment severity. In severe conditions, β-O-4 linked S units are more degraded than their G homologues.