An acid-free organosolv process was proposed to overcome the problems caused by acid catalyst in organosolv process, thereby producing ethanol from Liriodendron tulipifera effectively. Although relative lignin contents were above 20%, enzymatic conversion increased significantly to 65% at all conditions, and thus correlation between lignin and enzymatic conversion could not be explained using relative lignin content. Enzymatic conversion increased significantly above 65% regardless of temperature, which suggests the organosolv pretreatment with sodium hydroxide can be performed at lower temperature. FE-SEM showed that the process made the structure loose and broke down biomass through lignin dissolution. Wrinkle formation by alkaline swelling was also observed and it might increase surface area. Although pore-volume increased slightly, it was not the sole key factor for the organosolv pretreatment with sodium hydroxide. Increase in surface area and enzyme adsorption enhanced the enzymatic hydrolysis. Ethanol of 96% could be produced theoretically and it suggested that the acid-free organosolv process was an effective pretreatment method for bioethanol production from L. tulipifera. (C) 2011 Elsevier Ltd. All rights reserved.