This work aims to study the effects of Deep Eutectic Solvents (DES) on cellulosic fibre structure. A focus was made on the induced fibrillation phenomena which could facilitate the further production of microfibrillated cellulose. Three DES of different pH (acid, neutral and alkaline), namely betaine hydrochloride-urea, choline chloride-urea and choline chloride-monoethanolamine, were tested. Eucalyptus and cotton pulps were used to investigate the effects of DES on both hemicelluloses and cellulose. Interestingly, cellulose was esterified during acidic DES treatment. Moreover, an internal and external fibrillation occurred with DES treatment without a great extent of modification in terms of chemical composition, crystallinity and degree of polymerisation. Compared to enzymatic hydrolysis (used as a conventional pre-treatment for cellulose microfibrillation), DES have significantly enhanced the mechanical properties of resulting papers. To conclude, DES treatment can be considered as a soft and green “chemical” refining that could be applied as a pre-treatment for cellulose microfibrillation.