Volatile organic compounds emitted from historical books made from cotton/linen rag and wood pulp paper have been studied. Different profiles were obtained using different solid-phase microextraction (SPME) fibres to access the compounds involved in the decomposition reactions occurring in cotton/linen rag and wood pulp paper upon natural ageing and precocious/accelerated degradation. Contact head-space solid-phase extraction coupled with gas chromatography/time-of-flight mass spectrometry (GC-TOF-MS) was improved as a non-destructive methodology for the analysis of historical books. Potential markers of cellulose degradation-linear hydrocarbons, linear aldehydes, and 2-furfural-together with potential markers of cotton/linen rag paper (isopropylic esters) were identified. Chiral analysis (SPME-c-GC-TOF-MS) showed that only the enantiomer (S)-2-ethyl-1-hexanol is present as an emanation compound in both types of paper. Validation studies for a larger number of books are being done.