In this study, cornstalk was pretreated by an acid-chlorite delignification procedure to enhance the conversion of cornstalk to bio-oil in hot-compressed water liquefaction. The effects of the pretreatment conditions on the compositional and structural changes of the cornstalk and bio-oil yield were investigated. It was found that acid-chlorite pretreatment changed the main components and physical structures of cornstalk and effectively enhanced the bio-oil yield. Shorter residence time favored production of the total bio-oil products, whereas longer time led to cracking of the products. A high water loading was found to be favorable for high yields of total bio-oil and water-soluble oil. GC-MS analysis showed that the water-soluble oil and heavy oil were the complicated products of C(5-10) and C(8-11) organic compounds.