Green liquor (Na2S + Na2CO3, GL) pretreatment is a proven pathway to improve the enzymatic saccharification for the production of bioethanol. In this work, the effects of GL pretreatment on the chemical composition and enzymatic digestibility of rice straw at various total titratable alkali (TrA) charge and temperature were investigated. The GL pretreatment showed excellent performance in high polysaccharides retention and delignification selectivity. Under the optimized GL pretreatment condition (4% TrA charge, 20% sulfidity and 140 degrees C), 92.5% of glucan, 82.4% of xylan and 81.6% of arabinan in rice straw were recovered with a delignification of 39.4%. The maximum sugar yields of 83.9%, 69.6% and 78.0%, respectively for glucan, xylan and total sugar, were achieved at the same GL pretreatment condition with an enzyme loading of 40 FPU/g-substrate. The results suggested that GL pretreatment is a practicable method for rice straw to enhance enzymatic saccharification for bioethanol production. (C) 2013 Elsevier Ltd. All rights reserved.