The objective of this study was to characterise the anaerobic degradation of three paper mill waste water treatment residues in the shape of sludges and to correlate this anaerobic digestion to the physico-chemical characteristics of the paper sludges. After a deep characterisation of each paper sludge in their initial stage, several parameters were analysed on each paper sludge in mesophilic conditions for 40–50 days: pH, conductivity, chemical oxygen demand, total organic acids and organic fibres degradation. A special care was taken to identify and quantify the volatile fatty acids (VFAs) produced by the digestion using gas chromatography coupled with a mass spectrometer. The results showed that in paper sludges, cellulose mainly degrades over time while the degradation of the other fibres (hemicellulose and lignin) is limited. Consequently, the greater the cellulose content in a paper sludge, the greater the digestion and formation of VFAs. However, not all the cellulose degrades because of a shielding effect of lignin on cellulose, and a pH buffering effect of the calcium carbonate present in the paper sludges limits the hydrolysis-acidogenesis step of the anaerobic digestion. Finally, the gas chromatography–mass spectrometry (GC-MS) investigations showed that acetic acid is the main VFA produced by the anaerobic digestion of paper sludges. This work helps predicting paper mill sludge evolution in the purpose of using them in circular economy.