In this study, Eucalyptus camaldulensis was pretreated with 0.02 M aluminum chloride (AlCl3) at 140-180 degrees C to obtain digestible substrates for glucose and lignin. The effects of AlCl3-catalyzed hydrothermal pretreatment on the degradation of carbohydrates, structural changes of lignin, crystallinity, morphologic changes, and cellulose conversion of the pretreated biomass have been investigated by HAPEC, HPLC, FTIR, XRD, CP/MAS NMR, SEM, and 2D-HSQC NMR. Results showed that the pretreatment significantly removed hemicelluloses and cleaved beta-O-4 linkages of lignin at high temperatures. Under an optimum condition (at 170 degrees C for 1 h), almost all of hemicelluloses were removed and most of beta-O-4 linkages in lignin were cleaved, and 77.8% cellulose conversion of the pretreated biomass was achieved, which was 7.3-fold higher than that of the original biomass. In short, this process was regarded as a promising approach to achieve an efficient conversion of lignocellulosic biomass to fermentable glucose and residual lignin. (C) 2016 Elsevier Ltd. All rights reserved.