Calcium peroxide (CaO2) pretreatment was employed to remove lignin and subsequently facilitate enzymatic digestibility of wheat straw. An optimal condition was obtained at 130°C for 10 min with 0.35 g CaO2/g dried material of wheat straw and a 1:8 solid-liquid ratio. Under this condition, 57.8% of initial lignin, 7.2% of initial glucan, and 30.6% of initial xylan were removed from CaO2 pretreatment, respectively, meanwhile, a glucose recovery of 90.6 % and a xylose recovery of 65.9 % were obtained from the subsequent enzymatic hydrolysis of treated wheat straw, respectively. CaO2 pretreatment was proved to be a very effective method in delignification and improving enzymatic digestibility. Compared to raw material, the complex structure of lignocellulose was drastically disrupted with a wide emergence of scaly bulges and fully exposed microfibers, which still retained in the solid.