Eucommia ulmoides Oliver (EU) wood was successively treated by a combined system based on steam explosion pretreatment (SEP) and alkaline hydrogen peroxide post-treatment (AHPP). In this case, SEP was to disrupt the lignocellulosic structure, and the subsequent AHPP process was to isolate the high-purity lignin and cellulose-rich substrates. Results showed that the lignin fractions obtained during the AHPP exhibited smaller molecular weights, narrow polydispersity, less phenolic OH groups and lower syringyl/guaiacyl ratios (S/G) than those of the milled wood lignin (SEMWL) obtained from the only steam exploded EU. NMR characterization of lignin revealed that the AHPP process has a slight effect on the composition and molecular characteristic of lignin, and the lignin isolated had lower amounts of substructures (aryl-beta-ether, resinol, and phenylcoumaran linkages) as compared to those in SEMWL. Moreover, the subsequent SEP followed by AHPP process enhanced the enzymatic hydrolysis of cellulose-rich substrates to a maximum value of 91.69%. It was found that the synergistic treatment removed most of lignin, degraded hemicelluloses, and incurred a higher crystalline index and surface area of the cellulose-rich substrates as compared to the only steam explosion pretreatment. The combination of the SEP and AHPP processes is an environmentally benign and advantageous scheme for the production of high-purity lignin and cellulose-rich substrates, which will be further transformed into the value-added biomaterials and bioethanol. (C) 2015 Elsevier Ltd. All rights reserved.