•Development of the first detailed pyrolysis database for sheep and camel wool.•Interpretation of the pyrolysis profiles of the keratin proteins in wool.•Characterization of wool samples and historical threads by Double Shot Py-GC/MS and EGA/MS.•Evaluation of the relevant parameters affecting wool degradation. Wool has been the most widely used textile fiber in Europe since the Iron Age. It was largely employed to weave fabrics and clothes, and also for artistic purposes such as producing tapestries. This kind of artworks is among the most fragile of our heritage and is often in bad preservation conditions. Thus, the knowledge on the degradation processes of wool fibers is crucial for conservation issues. In the present study, we tested the potentialities of Pyrolysis coupled with Gas Chromatography and Mass Spectrometry (Py-GC/MS) and Evolved Gas Analysis coupled to Mass Spectrometry (EGA/MS) for the characterization of woolen reference samples, also subjected to artificial ageing, and of historical and archeological samples. The reference sheep wool yarns were prepared with different mordants and dyes, and have been analyzed both after storage in the dark for three years after preparation, and artificially aged for different time intervals and at different relative humidity values. We created a detailed pyrolysis database, evidencing the phenomena occurring with ageing and including camel wool for comparison. The ageing process undergone by the proteinaceous fraction of wool has also been investigated through monitoring specific fragment ions in the EGA profiles. The relevant parameters affecting the degradation process identified in this study match those assessed in previous investigations by different and complementary techniques, thus validating our approach. We proved that the novel approach based on EGA/MS is suitable for quickly assessing the conservation conditions of the woolen yarns and represents an advantage with respect to more time-consuming and complex methods, such as GC/MS or High Performance Liquid Chromatography (HPLC).