The supramolecular structure of four model celluloses was altered prior to their enzymatic saccharification using two ionic liquid pretreatments: one with the commonly used 1-ethyl-3-methylimidazolium acetate ([Emim]<SUP>+</SUP>[CH<SUB>3</SUB>COO]<SUP>-</SUP>) and the other with the newly developed 1-ethyl-3-methylimidazolium methylphosphonate ([Emim]<SUP>+</SUP>[MeO(H)PO<SUB>2</SUB>]<SUP>-</SUP>). The estimation of crystallinity index (CrI) by solid state <SUP>13</SUP>C nuclear magnetic resonance for each untreated/pretreated celluloses was compared with the performances of their enzymatic hydrolysis. For α-cellulose, both pretreatments led to a significant decrease in CrI from 25% to 5% but had no effect on glucose yields. In contrast, The [Emim]<SUP>+</SUP>[MeO(H)PO<SUB>2</SUB>]<SUP>-</SUP> pretreatment on the long fibers of cellulose had no significant effect on the CrI although a conversion yield in glucose of 88% is obtained versus 32% without pretreatment. However, scanning electron microscopy analysis suggested a loss of fiber organization induced by both ionic liquid pretreatments leading to a larger accessibility by cellulases to the cellulose surface.