A combined study of crystallinity index (CI), degree of polymerisation (DP) and thermal stability of cellulose was carried out for monitoring the effect of ball-milling. DP and CI are two fundamental quantities that describe the physico-chemical behaviour of cellulose. Milling is a common strategy to reduce cellulose crystallinity. In this work, four different commercially available celluloses were milled at 30, 60 and 120 min, and the changes in DP and CI were monitored using spectroscopic, diffraction and chromatographic techniques. Evolved gas analysis-mass spectrometry (EGA-MS) was also used to evaluate the changes in apparent activation energy (Ea) of the pyrolysis reaction upon different milling times by using model-free isoconversional methods. The results showed substantial decrease in CI values and moderate changes in DP after two-hours of ball-milling. Ea were found in the range 110-140 kJ/mol, and were reduced by 10% on average after two hours of ball-milling.