Microwave irradiation was employed as pretreatment for rice straw. The effects of microwave on enzymatic saccarification and lignocellulosic structure of rice straw, as well as its adsorption ability of enzyme, were investigated under the optimal conditions of pretreatment. The chemical composition analysis and structural properties determination by Fourier transform infrared spectroscopy and atomic force microscopy further confirmed that microwave pretreatment could disrupt the silicified waxy surface, break down lignin-hemicellulose complex and partially remove silicon and lignin, which could be favorable for the enhancement of enzymatic saccharification of rice straw and reduction of its adsorption of enzymes. However, X-ray diffraction analysis revealed that microwave irradiation had no significant influence on crystalline structure of cellulose.