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Sugarcane bagasse was pretreated by green liquor combined with ethanol (GL-Ethanol) and green liquor combined with H2O2 (GL-H2O2). After 72 h of enzymatic hydrolysis, the glucose yields of sugarcane bagasse pretreated with GL-Ethanol and GL-H2O2 were 97.7% and 41.7%, respectively. The reason that GL-Ethanol was more effective than GL-H2O2 has not been elucidated clearly. In this study, the chemical composition of the sugarcane bagasse and chemical structure of the isolated lignins after these two pretreatment methods were characterized to investigate their correlation with the enzymatic hydrolysis of sugarcane bagasse. The removal of lignins with GL-Ethanol pretreatment was much higher than that of GL-H2O2. In addition, the decomposition of cellulose was lower in the case of GL-Ethanol than in that of GL-H2O2. According to Fourier transform infrared spectroscopy (FT-IR) and 1H-nuclear magnetic resonance (NMR) studies, the ester bonds (belonging to lignin-carbohydrate complex) could be broken during GL-Ethanol treatment. It was also found that the molecular weight of lignins obtained from GL-Ethanol was lower than that of lignins from GL-H2O2.