Abstract: Microcrystalline cellulose samples with different crystallization index (Icr) were obtained by treatment with ionic liquids(ILs) 1-n-butyl-3-methylimidazolium chloride (Cl). The C1s spectra and O1s spectra from X-ray photoelectron spectroscopy (XPS)were adopted firstly to analyze the changes of crystallization index and chemical bonds in cellulose macro-molecule. Results showedgood accordance with the CP/MAS 13CNMR results. C2 peak of C1s XPS spectra and O1s1 peak of O1s XPS spectrahave close relation tohydrogen-bond in cellulose macromolecule, and their relative contents from peak area showed significant correlation with correlation coefficients of r1 0.9992 and r2 0.9679, respectively.