Sunflower stalks, a largely available and cheap agricultural residue lacking of economic alternatives, were subjected to steam explosion pretreatment, the objective being to optimize pre-treatment temperature in the range 180-230 degrees C. Enzymatic hydrolysis performed on the pre-treated solids by a cellulolytic complex (Celluclast 1.5 L) and analysis of filtrates were used to select the best pre-treatment temperature. Temperature selection was based on the susceptibility to enzymatic hydrolysis of the cellulose residue and both the cellulose recovery in the solid and the hemicellulose-derived sugars recoveries in the filtrate. After 96 h of enzymatic action, a maximum hydrolysis yield of 72% was attained in the water-insoluble fiber obtained after pre-treatment at 220 degrees C, corresponding to a glucose concentration of 43.7 g/L in hydrolysis media. Taking into account both cellulose recovery and hydrolysis yield, the maximum value of glucose yield referred to unpretreated raw material was also found when using steam pre-treated sunflower stalks at 220 degrees C, obtaining 16.7 g of glucose from 100 g of raw material. With regard to the filtrate analysis, most of the hemicellulosic-derived sugars released during the steam pre-treatment were in oligomeric form, the highest recovery being obtained at 210 degrees C pre-treatment temperature. Moreover, the utilisation of hemicellulosic-derived sugars as a fermentation substrate would improve the overall bioconversion of sunflower stalks into fuel ethanol. (C) 2007 Elsevier Inc. All rights reserved.