Rice straw is a lignocellulosic biomass, and has been recognized as a renewable organic substance and alternative energy source. In this study, rice straw was pretreated with hypochlorite-hydrogen peroxide (Ox-B) solution. The optimal pretreatment conditions were determined via response surface methodology, and the pretreated rice straw was hydrolyzed with exo-glucanase, endoglucanase, hemicellulase, and β-glucosidase Accellerase 1000™ (endo-glucanase equivalent activity of 1,250 carboxy methyl cellulose (CMC) U/g of rice straw pretreated for 24 h). The optimal conditions were as follows: 60 min pretreatment using Ox-B solution containing 0.6% hypochlorite and 25% hydrogen peroxide for 1 g of rice straw in a total reaction volume of 240 mL. Under these conditions, 406.8 mg of d-glucose and 224.0 mg of d-xylose were obtained from 1 g of rice straw. The fermentation of enzymatic hydrolysates containing 8.14 g/L d-glucose and 4.49 g/L d-xylose with Pichia stipitis generated 3.65 g/L of ethanol with a corresponding yield of 0.37 g/g. The maximum possible ethanol conversion rate is 72.54%.