This paper reports on the optimization of steam pretreatment of barley husk for high pentose and hexose recovery in the subsequent enzymatic hydrolysis step, as well as high ethanol yield, following simultaneous saccharification and fermentation. The parameters optimized in the steam pretreatment step were residence time (5-15 min), temperature (190-215 degreesC), and concentration of the acid catalyst (0 or 0.5% H2SO4). A microwave oven was employed for screening of the optimal conditions to obtain the highest sugar yield following combined pretreatment and enzymatic hydrolysis. The final optimization of the pretreatment prior to enzymatic hydrolysis was performed on a larger scale, in a steam pretreatment unit. Simultaneous saccharification and fermentation was carried out following steam pretreatment on 5 and 10% dry matter steam-pretreated slurries. Fermentability tests were performed to determine the effect of by-products (ie furfural and 5-hydroxymethyl furfural) in the bioconversion of glucose to ethanol by baker's yeast. The maximum glucose yield, 88% of the theoretical, was obtained following steam pretreatment with 0.5% H2SO4 at 200degreesC for 10 min. Under these conditions, a sugar to ethanol conversion of 81% was attained in simultaneous saccharification and fermentation. (C) 2004 Society of Chemical Industry.