AbstractAs an initial step in an alternative use of woody biomass to produce bioethanol, this work was aimed at investigating the effect of hot compressed water (HCW) pretreatment within the temperature range 100 to 200 °C in a batch-type reactor on the structural changes of Tamarix ramosissima. The untreated and pretreated solid residues were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), r transform infrared spectroscopy (FT-IR), solid-state cross polarization/magic angle spinning (CP/MAS), 13C NMR spectroscopy, and thermogravimetric analysis (TGA), as well as chemical methods. The results showed that HCW pretreatment solubilized mainly hemicelluloses and resulted in enriched cellulose and lignin content in the pretreated solids. It was found that the deposition of lignin droplets on the residual surfaces was produced during pretreatment under the hot water conditions above 140 °C. In addition, the removal of hemicelluloses and lignin re-localisation as a result of condensation reactions under the severe pretreatment condition may lead to an increase in cellulose crystallinity and thermal stability of biomass solid residues, thus consequently influencing the downstream digestibility of biomass for sugars and bioethanol production.