The present study highlights the development of a combined pretreatment and hydrolysis strategy of rice straw for the production of bioethanol and biopolymer (poly-3-hydroxybutyrate). Maximum reducing sugar yield was 0.374 g/g. The hydrolyzate is devoid of major fermentation inhibitors like furfural and organic acids and can be used for fermentation without any detoxification. Fermentation of the non-detoxified hydrolyzate with Saccharomyces cerevisiae yielded 1.48% of ethanol with a fermentation efficiency of 61.25% and with Comamonas sp. yielded 35.86% of poly-3-hydroxybutyrate without any nutrient supplementation. Characterization of native, control as well as the residue left out after combined pretreatment and hydrolysis of RS by scanning electron microscopy and X-ray diffraction showed difference. Compositional analysis revealed that the residue contains lignin and hemicellulose as the major component indicating that major portion of cellulose were hydrolyzed in this strategy. (C) 2016 Elsevier Ltd. All rights reserved.