Pretreatment method for rapeseed straw by sodium hydroxide was investigated for production of bioethanol and biobutanol. Various pretreatment parameters, including temperature, time, and sodium hydroxide concentration were optimized using a statistical method which is a central composite design of response surface methodology. In the case of sodium hydroxide pretreatment, optimal pretreatment conditions were found to be 7.9% sodium hydroxide concentration, 5.5 h of reaction time, and 68.4 °C of reaction temperature. The maximum glucose yield which can be recovered by enzymatic hydrolysis at the optimum conditions was 95.7% and the experimental result was 94.0 ± 4.8%. This experimental result was in agreement with the model prediction. An increase of surface area and pore size in pretreated rapeseed straw by sodium hydroxide pretreatment was observed by scanning electron microscope.