In this study, we aimed to dissolve microcrystalline cellulose (MCC) with phosphoric acid to obtain high-quality fermentable saccharides. MCC was directly dissolved in phosphoric acid (the concentration was 83%) for 10 hours at temperatures of 30, 50, and 70 degrees C. The structural changes of MCC were determined in detail with X-ray powder diffraction, solid-state cross-polarization magic angle spinning (13)C-NMR, and X-ray photoelectron spectroscopy. The kinetics of MCC decrystallization during treatment with phosphoric acid was also compared at 30, 50, and 70 degrees C. With the assumption of first order kinetics, the Arrhenius parameters of K, A(0) and E(a) were calculated. The rate constants of decrystallization reaction (K) were 0.06, 0.17, and 0.12 h(-1) respectively. The pre-exponential factor (A(0)) was 1.2 x 10(6) h(-1), and the activation energy (E(a)) was 42.4 kJ/mol.